Chemistry › Inorganic Chemistry

Synthesis and characterization of novel inorganic/organometallic compounds

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This cluster of papers explores the chemistry of main group elements and compounds, including the development of covalent radii, stable compounds, transition metal chemistry, and the use of N-heterocyclic carbene ligands. It also covers topics such as small molecule activation, catalysis, and the synthesis of p-conjugated materials.

Keywords

Main Group Chemistry; Covalent Radii; N-Heterocyclic Carbene; Stable Compounds; Transition Metal Chemistry; Divalent Carbon(0) Chemistry; Metalloid Clusters; p-Conjugated Materials; Small Molecule Activation; Catalysis

π-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New Millennium

2010-07-14

Roland C. Fischer , Philip P. Power

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTπ-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New MillenniumRoland C. Fischer*† and Philip P. Power*‡View Author Information … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTπ-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New MillenniumRoland C. Fischer*† and Philip P. Power*‡View Author Information Technische Universität Graz, Stremayrgasse 16/IV, A-8010, Graz, Austria, and University of California, Department of Chemistry, One Shields Avenue, Davis, California 95616* To whom correspondence should be addressed. E-mail: [email protected] (R.C.F.); [email protected] (P.P.P.).†Technische Universität Graz.‡University of California, Davis.Cite this: Chem. Rev. 2010, 110, 7, 3877–3923Publication Date (Web):July 14, 2010Publication History Received4 May 2010Published online14 July 2010Published inissue 14 July 2010https://pubs.acs.org/doi/10.1021/cr100133qhttps://doi.org/10.1021/cr100133qreview-articleACS PublicationsCopyright © 2010 American Chemical SocietyRequest reuse permissionsArticle Views15065Altmetric-Citations989LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Elements,Ligands,Molecular structure,Reaction products,Silicon Get e-Alerts

Acyl-und Alkylidenphosphane, XV 2.2-Dimethylpropylidinphosphan, eine stabile Verbindung mit einem Phosphoratom der Koordinationszahl 1/ Acyl- and Alkylidenephosphines, XV 2,2-Dimethylpropvlidynephosphine, a Stable Compound with a Phosphorus Atom of Coordination Number 1

1981-01-01

Gerd Becker , Gudrun Gresser , Werner Uhl

Abstract In the presence of small amounts of solid sodium hydroxide, [2,2-dimethyl-l-(trimethylsiloxy)propylidene]-trimethylsilylphosphine reacts at + 20 °C to give hexamethyldisiloxane and 2,2-dimethylpropylidynephosphine (2). In contrast to similar alkylidynephosphines this compound … Abstract In the presence of small amounts of solid sodium hydroxide, [2,2-dimethyl-l-(trimethylsiloxy)propylidene]-trimethylsilylphosphine reacts at + 20 °C to give hexamethyldisiloxane and 2,2-dimethylpropylidynephosphine (2). In contrast to similar alkylidynephosphines this compound is stable at room temperature. The IR and mass spectrum are discussed, and 1 H, 13 C and 31 P NMR spectral data are given.

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Towards a rigorously defined quantum chemical analysis of the chemical bond in donor–acceptor complexes

2003-03-01

Gernot Frenking

A Stable Silicon(0) Compound with a Si=Si Double Bond

2008-08-21

Yuzhong Wang , Yaoming Xie , Pingrong Wei +4 more

Dative, or nonoxidative, ligand coordination is common in transition metal complexes; however, this bonding motif is rare in compounds of main group elements in the formal oxidation state of zero. … Dative, or nonoxidative, ligand coordination is common in transition metal complexes; however, this bonding motif is rare in compounds of main group elements in the formal oxidation state of zero. Here, we report that the potassium graphite reduction of the neutral hypervalent silicon-carbene complex L:SiCl 4 {where L: is:C[N(2,6-Pr i 2 -C 6 H 3 )CH] 2 and Pr i is isopropyl} produces L:(Cl)Si–Si(Cl):L, a carbene-stabilized bis-silylene, and L:Si=Si:L, a carbene-stabilized diatomic silicon molecule with the Si atoms in the formal oxidation state of zero. The Si-Si bond distance of 2.2294 ± 0.0011 (standard deviation) angstroms in L:Si=Si:L is consistent with a Si=Si double bond. Complementary computational studies confirm the nature of the bonding in L:(Cl)Si–Si(Cl):L and L:Si=Si:L.

Polysilane high polymers

1989-09-01

Robert D. Miller , Josef Michl

ADVERTISEMENT RETURN TO ISSUEPREVArticlePolysilane high polymersRobert D. Miller and Josef MichlCite this: Chem. Rev. 1989, 89, 6, 1359–1410Publication Date (Print):September 1, 1989Publication History Published online1 May 2002Published inissue 1 September … ADVERTISEMENT RETURN TO ISSUEPREVArticlePolysilane high polymersRobert D. Miller and Josef MichlCite this: Chem. Rev. 1989, 89, 6, 1359–1410Publication Date (Print):September 1, 1989Publication History Published online1 May 2002Published inissue 1 September 1989https://pubs.acs.org/doi/10.1021/cr00096a006https://doi.org/10.1021/cr00096a006research-articleACS PublicationsRequest reuse permissionsArticle Views5676Altmetric-Citations1594LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Coordination chemistry at carbon

2009-06-14

Manuel Alcarazo , Christian W. Lehmann , Anakuthil Anoop +2 more

Metal complexes of weakly coordinating anions. Precursors of strong cationic organometallic Lewis acids

1988-11-01

Wolfgang Beck , Karlheinz Suenkel

ADVERTISEMENT RETURN TO ISSUEPREVArticleMetal complexes of weakly coordinating anions. Precursors of strong cationic organometallic Lewis acidsWolfgang Beck and Karlheinz SuenkelCite this: Chem. Rev. 1988, 88, 7, 1405–1421Publication Date (Print):November 1, … ADVERTISEMENT RETURN TO ISSUEPREVArticleMetal complexes of weakly coordinating anions. Precursors of strong cationic organometallic Lewis acidsWolfgang Beck and Karlheinz SuenkelCite this: Chem. Rev. 1988, 88, 7, 1405–1421Publication Date (Print):November 1, 1988Publication History Published online1 May 2002Published inissue 1 November 1988https://pubs.acs.org/doi/10.1021/cr00089a017https://doi.org/10.1021/cr00089a017research-articleACS PublicationsRequest reuse permissionsArticle Views3095Altmetric-Citations426LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

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The polysilane high polymers

1986-02-01

Robert West

Phosphaalkene, phospholyl and phosphinine ligands: New tools in coordination chemistry and catalysis

2005-11-29

P. Le Floch

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Facile Activation of Dihydrogen by an Unsaturated Heavier Main Group Compound

2005-08-16

Geoffrey H. Spikes , James C. Fettinger , Philip P. Power

The germanium alkyne analogue Ar'GeGeAr' (1, Ar' = C6H3-2,6(C6H3-2,6-Pri2)2) reacts with 1, 2, or 3 equiv of dihydrogen at room temperature, and at 1 atm pressure, to afford a mixture … The germanium alkyne analogue Ar'GeGeAr' (1, Ar' = C6H3-2,6(C6H3-2,6-Pri2)2) reacts with 1, 2, or 3 equiv of dihydrogen at room temperature, and at 1 atm pressure, to afford a mixture of the products Ar'HGeGeHAr' (2), Ar'H2GeGeH2Ar' (3), or Ar'GeH3 (4). The relative amounts of each product are governed by the number of equivalents of hydrogen used. A mechanism for the initial step in the reaction is proposed. The appearance of 4 among the reaction products was accounted for in terms of either its dissociation to monomers or isomerization to the bridged Ar'Ge(mu-H)2GeAr'. The reactions were monitored by 1H NMR spectroscopy. The products 2, 3, and 4 were characterized by X-ray crystallography, and 4 was synthesized independently by the reduction of Ar'Ge(OMe)3. These reactions represent the first direct addition of hydrogen to a closed shell unsaturated main group compound under ambient conditions.

Carbodiphosphoranes: The Chemistry of Divalent Carbon(0)

2006-10-31

Ralf Tonner , F. Oxler , B. Neumüller +2 more

A combined experimental/theoretical study gives strong evidence that carbodiphosphoranes are divalent carbon(0) compounds. The calculations show that carbodiphosphoranes have two lone pairs of electrons (see picture), which give rise to … A combined experimental/theoretical study gives strong evidence that carbodiphosphoranes are divalent carbon(0) compounds. The calculations show that carbodiphosphoranes have two lone pairs of electrons (see picture), which give rise to unusual properties as confirmed by experiment. The synthesis of a triply charged molecules in which two protonated carbodiphosphoranes serve as donor ligands to an Ag+ center supports the bonding model.

Tetramesityldisilene, a Stable Compound Containing a Silicon-Silicon Double Bond

1981-12-18

Robert West , Mark J. Fink , Josef Michl

Irradiation of 2,2-bis(2,4,6-trimethylphenyl)hexamethyltrisilane in hydrocarbon solution produces tetramesityldisilene, which can be isolated as a yellow-orange solid stable to room temperature and above in the absence of air. Like the olefins … Irradiation of 2,2-bis(2,4,6-trimethylphenyl)hexamethyltrisilane in hydrocarbon solution produces tetramesityldisilene, which can be isolated as a yellow-orange solid stable to room temperature and above in the absence of air. Like the olefins of carbon chemistry, tetramesityldisilene undergoes addition reactions across the silicon-silicon double bond.

Chemical Bonding in Higher Main Group Elements

1984-04-01

Werner Kutzelnigg

Abstract Many concepts used for a qualitative description of chemical bonding that originated in the early days of theoretical chemistry have been vindicated recently by quantum chemical calculations, at least … Abstract Many concepts used for a qualitative description of chemical bonding that originated in the early days of theoretical chemistry have been vindicated recently by quantum chemical calculations, at least as far as first row elements are concerned. However, many concepts that have been justified for first row elements (Li to Ne) cannot—contrary to widespread belief—be generalized to the higher main group elements. This applies particularly to the concept of hybridization, which should be viewed with considerable caution. The essential difference between the atoms of the first and higher rows is that the cores of the former contain only s‐AOs, whereas the cores of the latter include at least s‐ and p‐AOs. As a consequence, the s and p valence AOs of first row atoms are localized in roughly the same region of space, while the p valence AOs of higher row atoms are much more extended in space. This has the consequence that for the light main group elements both lone‐pair repulsion and isovalent hybridization play a greater role than for the heavy main group elements. Furthermore, this implies that single bonds between first row elements are weak and multiple bonds are strong, whereas for the second or higher row elements single bonds are strong and multiple bonds weak. The “extended valence” (violation of the octet rule) observed in compounds of higher main group elements has very little to do with the availability of d‐AOs but is due rather to the size of these atoms and thus to the reduced steric hindrance between ligands and, to a lesser extent, also to the lower electronegativity of the heavy atoms. A model based on the concept of electron‐rich multicenter bonds is certainly closer to reality than one involving hybrids with the participation of d‐AOs. The XO bonds in phosphane oxides, sulfoxides, oxo acids and related compounds are better formulated as semipolar rather than as true double bonds, even if they behave in some respects like double bonds.—The growing interest of theorists in compounds of higher main group elements parallels new and, in some instances, spectacular results of experimental research on the chemistry of these elements.

Zwitterionic and Donor-Stabilized N-Heterocyclic Silylenes (NHSis) for Metal-Free Activation of Small Molecules

2011-03-04

Shenglai Yao , Yun Xiong , Matthias Drieß

This account describes recent progress (>2006) in the synthesis and structural characterization of isolable N-heterocyclic silylenes (NHSi's) and their fascinating reactivities with respect to an emergent topic in main-group chemistry: … This account describes recent progress (>2006) in the synthesis and structural characterization of isolable N-heterocyclic silylenes (NHSi's) and their fascinating reactivities with respect to an emergent topic in main-group chemistry: metal-free small-molecule activation. Since the seminal discovery of stable N-heterocyclic silicon analogues of nucleophilic Wanzlick−Arduengo-type carbenes in 1994, new types of NHSi's have emerged with unique electronic features and strikingly different reactivities. Among them, the first zwitterionic (ylide-like) silylene LSi: (L = CH[(C═CH2)CMe][NAr]2; Ar = 2,6-Pri2C6H3) and unprecedented N-heterocyclic bis(silylenes) with amidinate ligands and Si(I)−Si(I) bonds were synthesized. Their striking electronic structures open new doorways to metal-free activation of C−H, C−X, Si−X, E−H (E = group 15, group 16 elements), P−P, E−O (E = C, N), and E−E bonds (E = O, S, Se, Te).

Silicon in organic synthesis

1978-01-01

Ernest W. Colvin

E. W. Colvin, Chem. Soc. Rev., 1978, 7, 15 DOI: 10.1039/CS9780700015 E. W. Colvin, Chem. Soc. Rev., 1978, 7, 15 DOI: 10.1039/CS9780700015

Über neue organische Phosphorverbindungen III. Phosphinmethylenderivate und Phosphinimine

1919-01-01

H. Staudinger , Jules Meyer

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Carbene-Stabilized Diphosphorus

2008-10-21

Yuzhong Wang , Yaoming Xie , Pingrong Wei +4 more

The potassium graphite reduction of L:PCl3 leads to the formation of carbene-stabilized diphosphorus molecules, L:P−P:L, 1 (L: = :C{N(2,6-Pr i 2C6H3)CH}2) and 2 (L: = :C{N(2,4,6-Me3C6H2)CH}2), respectively. The nature of … The potassium graphite reduction of L:PCl3 leads to the formation of carbene-stabilized diphosphorus molecules, L:P−P:L, 1 (L: = :C{N(2,6-Pr i 2C6H3)CH}2) and 2 (L: = :C{N(2,4,6-Me3C6H2)CH}2), respectively. The nature of the bonding in 1 and 2 was delineated by DFT computations.

The Tetrameric Aluminum(<scp>I</scp>) Compound [{Al(η5‐C5Me5)}4]

1991-05-01

Carsten Dohmeier , Christian Robl , Matthias Tacke +1 more

The tetrameric, η5-coordinated aluminum(I) compound [{Al(C5Me5)}4] (1) is stable at room temperature. It was prepared from AlCl and [Mg(C5Me5)2]. In this cluster, four Al atoms form a regular tetrahedron and … The tetrameric, η5-coordinated aluminum(I) compound [{Al(C5Me5)}4] (1) is stable at room temperature. It was prepared from AlCl and [Mg(C5Me5)2]. In this cluster, four Al atoms form a regular tetrahedron and the planes of the C5Me5 rings lie nearly parallel to the respective faces of the tetrahedron. (see also Highlight on p. 544).

Main-group elements as transition metals

2010-01-01

Philip P. Power

Divalent Carbon(0) Chemistry, Part 1: Parent Compounds

2008-03-03

Ralf Tonner , Gernot Frenking

Quantum-chemical calculations with DFT (BP86) and ab initio methods [MP2, SCS-MP2, CCSD(T)] have been carried out for the molecules C(PH(3))(2) (1), C(PMe(3))(2) (2), C(PPh(3))(2) (3), C(PPh(3))(CO) (4), C(CO)(2) (5), C(NHC(H))(2) … Quantum-chemical calculations with DFT (BP86) and ab initio methods [MP2, SCS-MP2, CCSD(T)] have been carried out for the molecules C(PH(3))(2) (1), C(PMe(3))(2) (2), C(PPh(3))(2) (3), C(PPh(3))(CO) (4), C(CO)(2) (5), C(NHC(H))(2) (6), C(NHC(Me))(2) (7) (Me(2)N)(2)C=C=C(NMe(2))(2) (8), and NHC (9), where NHC=N-heterocyclic carbene and NHC(Me)=N-methyl-substituted NHC. The electronic structure in 1-9 was analyzed with charge- and energy-partitioning methods. The results show that the bonding situations in L(2)C compounds 1-8 can be interpreted in terms of donor-acceptor interactions between closed-shell ligands L and a carbon atom which has two lone-pair orbitals L-->C<--L. This holds particularly for the carbodiphosphoranes 1-3 where L=PR(3), which therefore are classified as divalent carbon(0) compounds. The NBO analysis suggests that the best Lewis structures for the carbodicarbenes 6 and 7 where L is a NHC ligand have C==C==C double bonds as in the tetraaminoallene 8. However, the Lewis structures of 6-8, in which two lone-pair orbitals at the central carbon atom are enforced, have only a slightly higher residual density. Visual inspection of the frontier orbitals of the latter species reveals their pronounced lone-pair character, which suggests that even the quasi-linear tetraaminoallene 8 is a "masked" divalent carbon(0) compound. This explains the very shallow bending potential of 8. The same conclusion is drawn for phosphoranylketene 4 and for carbon suboxide (5), which according to the bonding analysis have hidden double-lone-pair character. The AIM analysis and the EDA calculations support the assignment of carbodiphosphoranes as divalent carbon(0) compounds, while NHC 9 is characterized as a divalent carbon(II) compound. The L-->C((1)D) donor-acceptor bonds are roughly twice as strong as the respective L-->BH(3) bond.

A Stable Compound Containing a Silicon-Silicon Triple Bond

2004-09-16

Akira Sekiguchi , Rei Kinjo , Masaaki Ichinohe

The reaction of 2,2,3,3-tetrabromo-1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasilane with four equivalents of potassium graphite (KC8) in tetrahydrofuran produces 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyl-2-tetrasilyne, a stable compound with a silicon-silicon triple bond, which can be isolated as emerald green … The reaction of 2,2,3,3-tetrabromo-1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasilane with four equivalents of potassium graphite (KC8) in tetrahydrofuran produces 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyl-2-tetrasilyne, a stable compound with a silicon-silicon triple bond, which can be isolated as emerald green crystals stable up to 100 degrees C in the absence of air. The SiSi triple-bond length (and its estimated standard deviation) is 2.0622(9) angstroms, which shows half the magnitude of the bond shortening of alkynes compared with that of alkenes. Unlike alkynes, the substituents at the SiSi group are not arranged in a linear fashion, but are trans-bent with a bond angle of 137.44(4) degrees.

A Stable Two-Coordinate Acyclic Silylene

2012-03-23

Andrey V. Protchenko , Krishna Hassomal Birjkumar , Deepak Dange +6 more

Simple two-coordinate acyclic silylenes, SiR(2), have hitherto been identified only as transient intermediates or thermally labile species. By making use of the strong σ-donor properties and high steric loading of … Simple two-coordinate acyclic silylenes, SiR(2), have hitherto been identified only as transient intermediates or thermally labile species. By making use of the strong σ-donor properties and high steric loading of the B(NDippCH)(2) substituent (Dipp = 2,6-(i)Pr(2)C(6)H(3)), an isolable monomeric species, Si{B(NDippCH)(2)}{N(SiMe(3))Dipp}, can be synthesized which is stable in the solid state up to 130 °C. This silylene species undergoes facile oxidative addition reactions with dihydrogen (at sub-ambient temperatures) and with alkyl C-H bonds, consistent with a low singlet-triplet gap (103.9 kJ mol(-1)), thus demonstrating fundamental modes of reactivity more characteristic of transition metal systems.

The isomers of silacyclopropane

1980-11-01

Mark S. Gordon

Looking for Stable Carbenes: The Difficulty in Starting Anew

1999-08-21

Anthony J. Arduengo

ADVERTISEMENT RETURN TO ISSUEArticleNEXTLooking for Stable Carbenes: The Difficulty in Starting AnewAnthony J. ArduengoView Author Information Institut für Anorganische und Analytische Chemie, der Technischen Universität Carolo-Wilhelmina, D-38106 Braunschweig, Germany Cite … ADVERTISEMENT RETURN TO ISSUEArticleNEXTLooking for Stable Carbenes: The Difficulty in Starting AnewAnthony J. ArduengoView Author Information Institut für Anorganische und Analytische Chemie, der Technischen Universität Carolo-Wilhelmina, D-38106 Braunschweig, Germany Cite this: Acc. Chem. Res. 1999, 32, 11, 913–921Publication Date (Web):August 21, 1999Publication History Received10 May 1999Published online21 August 1999Published inissue 1 November 1999https://pubs.acs.org/doi/10.1021/ar980126phttps://doi.org/10.1021/ar980126presearch-articleACS PublicationsCopyright © 1999 American Chemical SocietyRequest reuse permissionsArticle Views7133Altmetric-Citations1082LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Carbene compounds,Electron density,Isolation,Nitrogen,Substituents Get e-Alerts

Synthesis and Structure of a Stable Silylene

1994-03-01

Michael Denk , Robert P. Lennon , Randy K. Hayashi +6 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and Structure of a Stable SilyleneMichael Denk, Robert Lennon, Randy Hayashi, Robert West, Alexander V. Belyakov, Hans P. Verne, Arne Haaland, Matthias Wagner, and Nils MetzlerCite … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and Structure of a Stable SilyleneMichael Denk, Robert Lennon, Randy Hayashi, Robert West, Alexander V. Belyakov, Hans P. Verne, Arne Haaland, Matthias Wagner, and Nils MetzlerCite this: J. Am. Chem. Soc. 1994, 116, 6, 2691–2692Publication Date (Print):March 1, 1994Publication History Published online1 May 2002Published inissue 1 March 1994https://pubs.acs.org/doi/10.1021/ja00085a088https://doi.org/10.1021/ja00085a088research-articleACS PublicationsRequest reuse permissionsArticle Views5130Altmetric-Citations692LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Synthesis and Structure of a Monomeric Aluminum(I) Compound [{HC(CMeNAr)2}Al] (Ar=2,6–iPr2C6H3): A Stable Aluminum Analogue of a Carbene

2000-12-01

Chunming Cui , Herbert W. Roesky , Hans‐Georg Schmidt +3 more

A monovalent aluminum monomer [{HC(CMeNAr)2}Al] was obtained by reduction of the corresponding aluminum(III) diiodide. The molecular structure shows a unique two-coordinate aluminum center and a planar heterocyclic Al-N-C-C-C-N six-membered ring … A monovalent aluminum monomer [{HC(CMeNAr)2}Al] was obtained by reduction of the corresponding aluminum(III) diiodide. The molecular structure shows a unique two-coordinate aluminum center and a planar heterocyclic Al-N-C-C-C-N six-membered ring system (see picture). A nonbonded lone pair of electrons on the Al atom indicates the Lewis base character of the aluminum center. Ar=2,6-iPr2C6H3.

Subvalent Group 4B metal alkyls and amides. Part I. The synthesis and physical properties of kinetically stable bis[bis(trimethysilyl)methyl]-germanium(II), -tin(II), and -lead(II)

1976-01-01

P. J. Davidson , David Harris , Michael F. Läppert

Two methods are described for the synthesis of the unusual bivalent Group 4B metal alkyls M[CH(SiMe3)2]2(M = Ge, Sn,or Pb)from Li[CH(SiMe3)2] indiethyl ether at 0 to –20°C and (a) the … Two methods are described for the synthesis of the unusual bivalent Group 4B metal alkyls M[CH(SiMe3)2]2(M = Ge, Sn,or Pb)from Li[CH(SiMe3)2] indiethyl ether at 0 to –20°C and (a) the metal(II) chloride (M = Sn or Pb) or (b) M[N(SiMe3)2]2(M = Ge or Sn). At ambient temperature in cyclohexane or benzene the solutions are yellow (Ge), red (Sn), or purple (Pb), and the compounds are monomeric and in a singlet electronic ground state. There are colour changes between the solid and the melt, and the compounds tend to become colourless at –196 °C. The crystal structure of the tin(II) alkyl shows a centrosymmetric dimer with a Sn–Sn bond (2.76 Å) similar in length to that in Sn2Ph6, and the two pairs of geminal alkyl groups in a mutually trans arrangement. The solid germanium compound is inferred to be structurally similar because of the presence of a strong polarised Raman line at 300 cm–1. The monomer is believed to be angular with three approximately sp2 hybridised orbitals at the metal, one of which is non-bonding; the dimer. with a SnSn bent double bond, is formed by overlap of the non-bonding orbital of each monomer unit with the orthogonal vacant pz orbital of the other.

Triple‐Bond Covalent Radii

2005-04-14

Pekka Pyykkö , Sebastian Riedel , Michael Patzschke

A system of additive covalent radii is proposed for sigma(2) pi(4) triple bonds involving elements from Be to E 112 (eka-mercury). Borderline cases with weak multiple bonding are included. Only … A system of additive covalent radii is proposed for sigma(2) pi(4) triple bonds involving elements from Be to E 112 (eka-mercury). Borderline cases with weak multiple bonding are included. Only the elements in Group 1, the elements Zn-Hg in Group 12 and Ne in Group 18 are then totally excluded. Gaps are left at late actinides and some lanthanides. The standard deviation for the 324 included data points is 3.2 pm.

Über die Einwirkung von Halogenphosphor auf Alkyl‐formanilide. Eine neue Methode zur Darstellung sekundärer und tertiärer p ‐Alkylamino‐benzaldehyde

1927-01-12

Anton Vilsmeier , Alexander Haack

Polymers and the Periodic Table: Recent Developments in Inorganic Polymer Science

1996-08-01

Ian Manners

Abstract Polysiloxanes [R 2 SiO] n , polyphosphazenes [R 2 PN] n , and polysilanes [R 2 Si] n illustrate that the incorporation of inorganic elements into a polymer main … Abstract Polysiloxanes [R 2 SiO] n , polyphosphazenes [R 2 PN] n , and polysilanes [R 2 Si] n illustrate that the incorporation of inorganic elements into a polymer main chain can lead to useful properties. These include low temperature flexibility, high thermal and oxidative stability, flame retardancy, novel forms of chemical reactivity, and intriguing electrical and optical characteristics arising from unusual electronic effects such as the delocalization of σ electrons. However, until recently, the development of inorganic polymer science has been held back by the synthetic problem of finding ways to join atoms of inorganic elements together into long chains. This review surveys many of the exciting advances in the field of inorganic polymers over the past decade and focuses mainly on the new inorganic polymer systems that have been prepared during this period. These include random‐network polysilynes, poly(carbophosphazene)s, sulfur–nitrogen–phosphorus polymers, poly(organooxothiazene)s, and, very recently, the first examples of polystannanes that possess a main chain of tin atoms. Transition metal based polymer science has also experienced a number of synthetic break‐throughs and new materials include high molecular weight metallocene‐based polymers, polymetallaynes incorporating elements such as iron, nickel, and rhodium, liquid crystalline organocobalt and organochromium polymers, and lanthanide‐based polymers.

Aromaticity of Phosphorus Heterocycles

2001-04-24

László Nyulászi

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAromaticity of Phosphorus HeterocyclesLászló NyulásziView Author Information Department of Inorganic Chemistry, Budapest University of Technology and Economics, H-1521 Budapest, Gellért tér 4, Hungary Cite this: Chem. Rev. … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAromaticity of Phosphorus HeterocyclesLászló NyulásziView Author Information Department of Inorganic Chemistry, Budapest University of Technology and Economics, H-1521 Budapest, Gellért tér 4, Hungary Cite this: Chem. Rev. 2001, 101, 5, 1229–1246Publication Date (Web):April 24, 2001Publication History Received11 September 2000Published online24 April 2001Published inissue 1 May 2001https://pubs.acs.org/doi/10.1021/cr990321xhttps://doi.org/10.1021/cr990321xresearch-articleACS PublicationsCopyright © 2001 American Chemical SocietyRequest reuse permissionsArticle Views4646Altmetric-Citations352LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Aromatic compounds,Aromaticity,Chemical structure,Phosphorus,Stabilization Get e-Alerts

Phospha‐Organic Chemistry: Panorama and Perspectives

2003-04-10

François Mathey

Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry … Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry of these compounds mimics the chemistry of their all-carbon analogues. In this Review article this analogy is discussed for the phosphorus counterparts of alkenes, alkynes, and carbenes. In each case, the synthesis, reactivity, and coordination modes are briefly examined. Some special electronic configurations are also discussed, which include one-electron Pbond;P bonds, strained bonds, and aromatic systems. To conclude, some potential applications of this chemistry in the areas of molecular materials and homogeneous catalysis are presented.

Lewis Base Stabilized Dichlorosilylene

2009-06-23

Rajendra S. Ghadwal , Herbert W. Roesky , Sebastian Merkel +2 more

Stable? You can bottle it! The base-stabilized dichlorosilylene L1SiCl2 (see picture; L1=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) is stable at room temperature. L1SiCl2 can undergo a reaction with diphenylacetylene to form a trisilacyclopentene derivative. These … Stable? You can bottle it! The base-stabilized dichlorosilylene L1SiCl2 (see picture; L1=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) is stable at room temperature. L1SiCl2 can undergo a reaction with diphenylacetylene to form a trisilacyclopentene derivative. These compounds have been characterized by X-ray crystallography and computational studies.

Insights on the Design and Electron-Acceptor Properties of Conjugated Organophosphorus Materials

2014-05-06

Thomas Baumgartner

The development of conjugated organic materials has become a rapidly evolving field of research, particularly with a view toward practical applications in so-called organic electronics that encompass a variety of … The development of conjugated organic materials has become a rapidly evolving field of research, particularly with a view toward practical applications in so-called organic electronics that encompass a variety of device types, such as OLEDs, OPVs, and OFETs. Almost all of these devices minimally require the presence of electron-donor and -acceptor components that act as p- and n-type semiconductors, respectively. Research over the past two decades has shown that while there is an abundant resource of organic p-type materials, suitable n-type species are few and far between. To overcome this severe bottleneck for the further development of organic electronics, researchers have identified organo-main-group avenues as valuable alternatives toward organic electron-acceptor materials that may ultimately be used as n-type components in practical devices. One particular element of interest in this context is phosphorus, which at first glance may not necessarily suggest such properties. In this Account, I provide detailed insights on the origin of the electron-acceptor properties of organophosphorus-based conjugated materials and include an overview of important molecular species that have been developed by my group and others. To this end, I explain that the electron-acceptor properties of conjugated organophosphorus materials originate from an interaction known as negative hyperconjugation. While this particular interaction creates a simply inductively withdrawing phosphoryl substituent for π-conjugated scaffolds, incorporation of a phosphorus atom as an integral part of a cyclic substructure within a π-conjugated system provides a much more complex, versatile, and consequently highly valuable tool for the tuning of the electron-acceptor properties of the materials. Notably, the degree of negative hyperconjugation can effectively be tailored in various ways via simple substitution at the phosphorus center. This is now well established for phosphole-based molecular materials, in which the electron-acceptor properties are also mirrored by the degree of antiaromaticity of the system. Particularly, fused and π-extended phosphole materials show appreciable electron-acceptor properties, evident in low reduction potentials and corresponding LUMO levels. But these features do not always translate into powerful n-type materials. My group and others have thus recently been focusing on molecular organophosphorus scaffolds that also involve incorporation of imino or carbonyl groups, next to the incorporation of low coordinate phosphorus centers, to achieve superior electron-acceptor features. This state-of-the-art research has confirmed the great potential of the organophosphorus route toward powerful electron-acceptor materials, but further work is required to also establish these species as functional n-type materials.

Carbene Stabilization of Highly Reactive Main-Group Molecules

2011-06-02

Yuzhong Wang , Gregory H. Robinson

This article highlights recent efforts of this laboratory in the stabilization of highly reactive, low-oxidation-state, main-group molecules using bulky N-heterocyclic carbene ligands [L: = :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2); L': = :C{N(2,4,6-Me(3)C(6)H(2))CH}(2); L'': = … This article highlights recent efforts of this laboratory in the stabilization of highly reactive, low-oxidation-state, main-group molecules using bulky N-heterocyclic carbene ligands [L: = :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2); L': = :C{N(2,4,6-Me(3)C(6)H(2))CH}(2); L'': = :C{(i-Pr)NC(Me)}(2)]. The syntheses, structures, and computational studies of carbene-stabilized neutral diborenes [L:(H)B═B(H):L and L':(H)B═B(H):L'], a neutral Ga(6) octahedron (L'':Ga[Ga(4)Mes(4)]Ga:L''), disilicon (L:Si═Si:L), bis-silylene [L:(Cl)Si-Si(Cl):L], dipnictogens (L:E-E:L, E = P, As; L':P-P:L'), and parent phosphinidene (L:PH) are discussed. Some of the unique challenges associated with this "carbene-stabilization" strategy are also presented.

Boron-pyrazole chemistry. IV. Carbon- and boron-substituted poly[(1-pyrazolyl) borates]

1967-11-01

Swiatoslaw Trofimenko

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTBoron-pyrazole chemistry. IV. Carbon- and boron-substituted poly[(1-pyrazolyl) borates]Swiatoslaw. TrofimenkoCite this: J. Am. Chem. Soc. 1967, 89, 24, 6288–6294Publication Date (Print):November 1, 1967Publication History Published online1 May 2002Published … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTBoron-pyrazole chemistry. IV. Carbon- and boron-substituted poly[(1-pyrazolyl) borates]Swiatoslaw. TrofimenkoCite this: J. Am. Chem. Soc. 1967, 89, 24, 6288–6294Publication Date (Print):November 1, 1967Publication History Published online1 May 2002Published inissue 1 November 1967https://pubs.acs.org/doi/10.1021/ja01000a053https://doi.org/10.1021/ja01000a053research-articleACS PublicationsRequest reuse permissionsArticle Views3622Altmetric-Citations327LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Scandium complex [{(.eta.5-C5Me4)Me2Si(.eta.1-NCMe3)}(PMe3)ScH]2: a unique example of a single-component .alpha.-olefin polymerization catalyst

1990-03-01

Pamela J. Shapiro , Emilio E. Bunel , William P. Schaefer +1 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTScandium complex [{(.eta.5-C5Me4)Me2Si(.eta.1-NCMe3)}(PMe3)ScH]2: a unique example of a single-component .alpha.-olefin polymerization catalystPamela J. Shapiro, Emilio Bunel, William P. Schaefer, and John E. BercawCite this: Organometallics 1990, 9, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTScandium complex [{(.eta.5-C5Me4)Me2Si(.eta.1-NCMe3)}(PMe3)ScH]2: a unique example of a single-component .alpha.-olefin polymerization catalystPamela J. Shapiro, Emilio Bunel, William P. Schaefer, and John E. BercawCite this: Organometallics 1990, 9, 3, 867–869Publication Date (Print):March 1, 1990Publication History Published online1 May 2002Published inissue 1 March 1990https://pubs.acs.org/doi/10.1021/om00117a055https://doi.org/10.1021/om00117a055research-articleACS PublicationsRequest reuse permissionsArticle Views2125Altmetric-Citations526LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

The First Isolable Dialkylsilylene

1999-09-29

Mitsuo Kira , Shintaro Ishida , Takeaki Iwamoto +1 more

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTThe First Isolable DialkylsilyleneMitsuo Kira, Shintaro Ishida, Takeaki Iwamoto, and Chizuko KabutoView Author Information Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan … ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTThe First Isolable DialkylsilyleneMitsuo Kira, Shintaro Ishida, Takeaki Iwamoto, and Chizuko KabutoView Author Information Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan Cite this: J. Am. Chem. Soc. 1999, 121, 41, 9722–9723Publication Date (Web):September 29, 1999Publication History Received19 July 1999Published online29 September 1999Published inissue 1 October 1999https://pubs.acs.org/doi/10.1021/ja9925305https://doi.org/10.1021/ja9925305rapid-communicationACS PublicationsCopyright © 1999 American Chemical SocietyRequest reuse permissionsArticle Views5401Altmetric-Citations408LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (2)»Supporting Information Supporting Information SUBJECTS:Resonance structures,Silicon,Substituents Get e-Alerts

The Chemistry of Aluminum(I), Silicon(II), and Germanium(II)

2008-02-01

Selvarajan Nagendran , Herbert W. Roesky

Although tetrameric Al(I) compounds have been known for a long time, the monomeric Al(I) compounds that are analogous to carbenes are very recent entrants in Al(I) chemistry. They possess novel … Although tetrameric Al(I) compounds have been known for a long time, the monomeric Al(I) compounds that are analogous to carbenes are very recent entrants in Al(I) chemistry. They possess novel structural features and exhibit distinct reactivity. This has resulted in the isolation and characterization of various unusual aluminum(III) compounds such as the aluminatetrazoles and aluminacyclopropenes. In comparison to the recent emergence of monomeric aluminum(I) compounds, stable silylenes and germylenes (carbene analogues of silicon and germanium) were recognized much earlier. This led to the evolution of the Si(II) and Ge(II) chemistry that at times surpasses the sophistication achieved in divalent carbon chemistry. Thus, while carbon lacks an example of a stable chlorocarbene (LCCl), for silicon there is one example of LSiCl, and for germanium there are a fair number of LGeCl compounds. While reactivity studies on LSiCl are anticipated, the utility of RGeCl as a synthon is well documented. Exotic compounds such as a germanethioacid chloride, a germanium(II) hydride, and a germanium(II) hydroxide are some of the examples that were derived from LGeCl. Recent results from our laboratory at Göttingen have helped in the development of these interesting areas of research, and the present account summarizes our contributions to the chemistry of Al(I), Si(II), and Ge(II).

Comprehensive Chemistry of Polycarbosilanes, Polysilazanes, and Polycarbosilazanes as Precursors of Ceramics

1995-07-01

Marc Birot , Jean‐Paul Pillot , J. DUNOGUÈS

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTComprehensive Chemistry of Polycarbosilanes, Polysilazanes, and Polycarbosilazanes as Precursors of CeramicsMarc Birot, Jean-Paul Pillot, and Jacques DunoguesCite this: Chem. Rev. 1995, 95, 5, 1443–1477Publication Date (Print):July 1, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTComprehensive Chemistry of Polycarbosilanes, Polysilazanes, and Polycarbosilazanes as Precursors of CeramicsMarc Birot, Jean-Paul Pillot, and Jacques DunoguesCite this: Chem. Rev. 1995, 95, 5, 1443–1477Publication Date (Print):July 1, 1995Publication History Published online1 May 2002Published inissue 1 July 1995https://pubs.acs.org/doi/10.1021/cr00037a014https://doi.org/10.1021/cr00037a014research-articleACS PublicationsRequest reuse permissionsArticle Views3288Altmetric-Citations455LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Coordination chemistry of lithium ion: a crystal and molecular structure review

1991-03-01

Uriel Olsher , Reed M. Izatt , Jerald S. Bradshaw +1 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCoordination chemistry of lithium ion: a crystal and molecular structure reviewUriel. Olsher, Reed M. Izatt, Jerald S. Bradshaw, and N. Kent. DalleyCite this: Chem. Rev. 1991, 91, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCoordination chemistry of lithium ion: a crystal and molecular structure reviewUriel. Olsher, Reed M. Izatt, Jerald S. Bradshaw, and N. Kent. DalleyCite this: Chem. Rev. 1991, 91, 2, 137–164Publication Date (Print):March 1, 1991Publication History Published online1 May 2002Published inissue 1 March 1991https://pubs.acs.org/doi/10.1021/cr00002a003https://doi.org/10.1021/cr00002a003research-articleACS PublicationsRequest reuse permissionsArticle Views6239Altmetric-Citations317LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

How to Read and Interpret FTIR Spectroscope of Organic Material

2019-03-07

Asep Bayu Dani Nandiyanto , Rosi Oktiani , Risti Ragadhita

Fourier Transform Infrared (FTIR) has been developed as a tool for the simultaneous and quantitative determination of organic components, including chemical bond, as well as organic content (e.g. protein, carbohydrate … Fourier Transform Infrared (FTIR) has been developed as a tool for the simultaneous and quantitative determination of organic components, including chemical bond, as well as organic content (e.g. protein, carbohydrate and lipid). However, until now, there is no further information for the detailed information in the FTIR peaks. The objective of this study was to demonstrate how to read and assess chemical bond and structure in the organic material. The analysis was then compared with the literatures. The step-by-step method on how to read the FTIR data was presented, including reviewing simple to the complex organic materials. This study is potential to be used as a standard information on how to read FTIR peaks in the biochemical and organic materials.

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Synthesis and structure of bis(2,4,6-tri-tert-butylphenyl)diphosphene: isolation of a true phosphobenzene

1981-07-01

Masaaki Yoshifuji , Ichiro Shima , Naoki Inamoto +2 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and structure of bis(2,4,6-tri-tert-butylphenyl)diphosphene: isolation of a true phosphobenzeneM. Yoshifuji, I. Shima, N. Inamoto, K. Hirotsu, and T. HiguchiCite this: J. Am. Chem. Soc. 1981, 103, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and structure of bis(2,4,6-tri-tert-butylphenyl)diphosphene: isolation of a true phosphobenzeneM. Yoshifuji, I. Shima, N. Inamoto, K. Hirotsu, and T. HiguchiCite this: J. Am. Chem. Soc. 1981, 103, 15, 4587–4589Publication Date (Print):July 1, 1981Publication History Published online1 May 2002Published inissue 1 July 1981https://pubs.acs.org/doi/10.1021/ja00405a054https://doi.org/10.1021/ja00405a054research-articleACS PublicationsRequest reuse permissionsArticle Views3851Altmetric-Citations772LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Silanes and Other Coupling Agents

2020-04-27

Phosphororganische Verbindungen, XX. Phosphinoxyde als Olefinierungsreagenzien

1959-10-01

Leopold Horner , Hellmut Hoffmann , Hans G. Wippel +1 more

Abstract Phosphinoxyde (und Phosphonate) mit einer zur PO‐Gruppierung nachbarständigen CH‐Gruppe setzen sich mit Aldehyden und Ketonen unter Mitwirkung von Basen — vorteilhaft Kalium‐tert.‐butylat — zu Olefinen um. Die Reaktion verläuft … Abstract Phosphinoxyde (und Phosphonate) mit einer zur PO‐Gruppierung nachbarständigen CH‐Gruppe setzen sich mit Aldehyden und Ketonen unter Mitwirkung von Basen — vorteilhaft Kalium‐tert.‐butylat — zu Olefinen um. Die Reaktion verläuft über die Stufe der β‐Hydroxy‐alkylphosphinoxyde. Ein Vertreter dieser Verbindungsklasse, auf einem übersichtlichen Weg synthetisiert, zerfällt in Anwesenheit von Kalium‐tert.‐butylat in Phosphinsäure und Olefin. — Mit Phenyl‐lithium in α‐Stellung metallierte Phosphinoxyde reagieren mit Carbonylverbindungen zu β‐Hydroxy‐alkylphosphinoxyden. Durch Umsetzung von Phosphinoxyden mit Carbonsäureestern und Kalium‐tert.‐butylat als Kondensationsmittel entstehen β‐Keto‐alkylphosphinoxyde.

Silane Coupling Agents

1991-01-01

Edwin P. Plueddemann

Intermetallische Verbindungen

1939-01-07

E. Zintl

The Chemistry of Organic Silicon Compounds

1998-07-30

Stable Silylenes

2000-07-21

Michael Haaf , Thomas A. Schmedake , Robert West

The field of stable silylene research has grown dramatically since the first isolation of a stable silylene in 1994. Prior to 1994, silylenes existed only as reactive intermediates, isolable only … The field of stable silylene research has grown dramatically since the first isolation of a stable silylene in 1994. Prior to 1994, silylenes existed only as reactive intermediates, isolable only in low-temperature matrixes. Since then, several stable silylenes have been synthesized, some in fact showing remarkable thermal stability. This Account highlights the developments in stable silylene chemistry, including theoretical and experimental studies attempting to explain the remarkable stability of the silylenes as well as the rapidly expanding reaction chemistry of the stable silylenes.

Cationic π-Stacked 3a,6a-Diaza-1,4-diphosphapentalenes (DDP): Tuning the Energy of Electronic Transitions by Changing the Interdeck Distance in a Triple-Decker DDP

2025-06-25

V.V. Sushev , Н. В. Золотарева , Alexandra Khristolyubova +4 more | Inorganic Chemistry

Double-decker dications of 3a,6a-diaza-1,4-diphosphapentalenes [(R1R2DDP)2]2+ (where R1R2 = peripheral substituents Me,Me; Et,Me; c-Hex-annelated) behave as π-acceptors when interacting with planar π-donor molecules. The interaction of double-decker ditriflates with free diazadiphosphapentalenes … Double-decker dications of 3a,6a-diaza-1,4-diphosphapentalenes [(R1R2DDP)2]2+ (where R1R2 = peripheral substituents Me,Me; Et,Me; c-Hex-annelated) behave as π-acceptors when interacting with planar π-donor molecules. The interaction of double-decker ditriflates with free diazadiphosphapentalenes leads to the formation of deeply colored EPR silent triple-decker compounds [(R1R2DDP)3]2+(TfO-)2. According to DFT calculations, the largest positive charge in the dication is concentrated on the phosphorus atoms of the middle deck. The UV-vis absorption spectra of the obtained compounds have absorption band maxima at 563, 619, and 670 nm for (MeMeDDP)3(OTf)2 (5), (EtMeDDP)3(OTf)2 (10), and (cHexDDP)3(OTf)2 (11), respectively. We explain such a significant difference in the energy of electron transitions by the different distances between the decks in the given compounds, caused by steric factors. DFT calculations using the dication [(MeMeDDP)3]2+ as an example showed that λmax shifts from 500 to 831 nm with an increase in the interdeck distance from 2.9 to 3.5 Å. Weaker π-donors─carbazole and dibenzothiophene─form one-dimensional stacks with the double-decker ditriflate (MeMeDDP)2(OTf)2, consisting of alternating donor and double-decker acceptor molecules.

Preparation and Characterization of Phosphazenium Trifluoromethylselanide and Trifluoromethyltellanide Salts Starting from HCF3

2025-06-24

Katharina Wels , Beate Neumann , H.-G. Stammler +1 more | Inorganic Chemistry

The deprotonation of HCF3, an industrial waste product, by the super basic phosphazene, {(Et2N)3P = N}3P = NtBu (EtP4), enables the syntheses and characterization of the trifluoromethylchalcogenide salts [EtP4H]+[SeCF3]- and … The deprotonation of HCF3, an industrial waste product, by the super basic phosphazene, {(Et2N)3P = N}3P = NtBu (EtP4), enables the syntheses and characterization of the trifluoromethylchalcogenide salts [EtP4H]+[SeCF3]- and [EtP4H]+[TeCF3]-. These salts were generated through nucleophilic trifluoromethylation of elemental selenium and tellurium. The use of HCF3 as a readily available and cheap CF3 source makes this an efficient and economical approach to trifluoromethylselanide and trifluoromethyltellanide salts. In addition to the structural elucidation of both salts, the reactivity of the selanide salt was explored, whereby the new gallium and indium species, [EtP4H]+[(C2F5)3GaSeCF3]- and [EtP4H]+[(C2F5)3InSeCF3]- were synthesized.

The Role of Elemental Factors in the Reactivity of Combination Reactions between Heavy Vinylidene-Like Molecules and Carbene Analogues

2025-06-18

Zhengfeng Zhang , Ming‐Der Su | Inorganic Chemistry

Utilizing the M06-2X-D3/def2-TZVP approach, we studied the capture reactions of carbene-like G14Br2 with NHC-supported vinylidene analogs, (NHC):→C═G14(Br)(Tbb) (G14-Rea; G14 = group 14 element). The findings indicate that the C═G14 double … Utilizing the M06-2X-D3/def2-TZVP approach, we studied the capture reactions of carbene-like G14Br2 with NHC-supported vinylidene analogs, (NHC):→C═G14(Br)(Tbb) (G14-Rea; G14 = group 14 element). The findings indicate that the C═G14 double bond is formed through electron-sharing interactions between the triplet (NHC):→C and triplet G14(Br)(Tbb) fragments for G14 elements including C, Si, Ge, Sn, and Pb. Our computational study suggests that only vinylidene analogs bearing C═Si and C═Ge double bonds can effectively capture GeBr2 and proceed through a 1,2-migration reaction. In contrast, only CBr2, SiBr2, and GeBr2 exhibit successful addition to the (NHC):→C═Ge(Br)(Tbb) double bond. Computational analyses reveal that in the capture reaction of G14Br2 by G14-Rea vinylidene analogs, bonding is primarily governed by a forward interaction (G14-Rea → G14Br2), while back-donation (G14-Rea ← G14Br2) plays a minor role. Shaik's model effectively demonstrates that the reaction barrier for capturing carbene-like G14Br2 molecules by NHC-supported vinylidene-like G14-Rea compounds is significantly influenced by the singlet-triplet energy splitting in G14-Rea or carbenic G14Br2 species. The reactivity trend and mechanistic behavior of the vinylidene-like system are systematically examined through the activation strain model of reactivity and energy decomposition analysis.

Zwitterionic Heavier Pnictinidenes in Redox Catalysis

2025-06-18

Selwin Fernando , Yi‐Chen Chan , Sergio Fernández +5 more | Angewandte Chemie

Herein we describe a new class of zwitterionic heavier pnictogen species with bis(N‐Heterocyclic Carbene)borate as ligands, enabling the isolation of stable Sb and Bi species in multiple oxidation states. Computational … Herein we describe a new class of zwitterionic heavier pnictogen species with bis(N‐Heterocyclic Carbene)borate as ligands, enabling the isolation of stable Sb and Bi species in multiple oxidation states. Computational analysis of zwitterionic pnictinidenes revealed their cationic character at the metal centre while holding unique electronic properties that contribute to their nucleophilicity and stability. These systems participate in oxidative addition and reductive elimination processes, and display redox catalytic activity in hydrodefluorination reactions, marking a unique example of cationic pnictinidene catalysing a redox transformation and providing reactivity beyond the constraints of pincer ligands. Additionally, we report on a novel dehydrogenative thiolation of silanes. This work expands the scope of low‐valent pnictogen chemistry, providing a novel platform for main group redox catalysis.

Zwitterionic Heavier Pnictinidenes in Redox Catalysis

2025-06-18

Selwin Fernando , Yi‐Chen Chan , Sergio Fernández +5 more | Angewandte Chemie International Edition

Valence and Oxidation State: A Comparison of Their Value and Limitations as Simple Chemical Models

2025-06-17

Nicholas C. Norman , Paul G. Pringle | Organometallics

On the Reaction of Pacman‐Phosphanes with Lewis Acids

2025-06-17

Leon Ohms , Pascal J. Schmidt , Jonas Surkau +2 more | Chemistry - A European Journal

The reactions of Pacman phosphanes (1a) with Lewis acids such as R3B (R = C6H5, C6F5) and GaCl3 was investigated. While equilibria between mono‐ and di‐adducts were found in the … The reactions of Pacman phosphanes (1a) with Lewis acids such as R3B (R = C6H5, C6F5) and GaCl3 was investigated. While equilibria between mono‐ and di‐adducts were found in the reaction with BPh3, B(C6F5)3 preferentially formed the di‐adduct (1a·2B(C6F5)3), which could be isolated and fully characterized. DFT calculations showed that the N‐bonded adducts are thermodynamically more stable than the P‐bonded adducts. In contrast to the reaction of the Pacman phosphane with boranes, GaCl3 reacted with 1a to give an unusual [Pacman‐GaCl2]+[GaCl4]– salt, featuring a nearly planar GaN2C2 heterocycle as part of the Pacman macrocycle. In addition, the coordination geometry on one P atom changes from triple to an unusual quadruple coordination, although it is still a formal P atom in the +III oxidation state, as shown by quantum chemical calculations.

A Linear Metallocene of Sc(II) Supported by [C5Me4(SiMe2tBu)]1– Ligands

2025-06-12

Joseph Q. Nguyen , Ahmadreza Rajabi , Anthony J. Wang +3 more | Journal of the American Chemical Society

Reduction of [C5Me4(SiMe2tBu)]2ScI with KC8 generates the first example of a neutral, linear metallocene of scandium analogous to ferrocene, namely [C5Me4(SiMe2tBu)]2Sc. X-ray diffraction studies, spectroscopic analyses, and DFT calculations are … Reduction of [C5Me4(SiMe2tBu)]2ScI with KC8 generates the first example of a neutral, linear metallocene of scandium analogous to ferrocene, namely [C5Me4(SiMe2tBu)]2Sc. X-ray diffraction studies, spectroscopic analyses, and DFT calculations are consistent with a Sc(II) complex. [C5Me4(SiMe2tBu)]2Sc reacts reversibly with N2 to provide the end-on (N═N)2- complex {[C5Me4(SiMe2tBu)]2Sc}2(μ-η1:η1-N2) and gives a rare example of a crystallographically characterizable Sc(III) terminal hydroxide, namely [C5Me4(SiMe2tBu)]2Sc(OH), as a hydrolysis product. The analogous linear Ca(II) metallocene [C5Me4(SiMe2tBu)]2Ca was synthesized and characterized for comparison.

Flash Communication: Metathesis of Heavy Alkyne Analogues in Solution via Dissociation of m-Terphenyl Substituted Distannynes and Diplumbynes

2025-06-10

Joshua D. Queen , Philip P. Power | Organometallics

Pnictogenium Ions as a Powerful Tool for the Synthesis of Three‐ and Five‐Membered Interpnictogen Chains

2025-06-09

Lisa Zimmermann , Robert Szlosek , Christian Scholtes +4 more | ChemistryEurope

The synthesis and characterization of novel three‐ and five‐membered interpnictogen chain compounds are presented. In a systematic study, the heterodipnictogen complexes [{CpMo(CO) 2 } 2 (μ,η 2:2 ‐EE′)] ( Mo … The synthesis and characterization of novel three‐ and five‐membered interpnictogen chain compounds are presented. In a systematic study, the heterodipnictogen complexes [{CpMo(CO) 2 } 2 (μ,η 2:2 ‐EE′)] ( Mo 2 PAs : E = P, E′ = As; Mo 2 PSb : E = P, E′ = Sb; Mo 2 AsSb : E = As, E′ = Sb) are reacted with in situ generated pnictogenium ions of a third pnictogen. Phosphenium ions insert into the AsSb bond of Mo 2 AsSb to give [{CpMo(CO) 2 } 2 (μ,η 1:1:1:1 ‐AsPPh 2 Sb)][TEF] ( 1 ) ([TEF] − = [Al{OC(CF 3 ) 3 } 4 ] − ). In contrast, arsenium, stibenium, and bismuthenium ions, respectively, coordinate to the phosphorus atom of Mo 2 PAs and Mo 2 PSb . The obtained complexes [{CpMo(CO) 2 } 2 (μ,η 2:2 ‐SbPAsCy 2 )][BArF 24 ] ( 2 ), [{CpMo(CO) 2 } 2 (μ,η 2:2 ‐AsPSbPh 2 )][BArF 24 ] ( 3 ), and [{CpMo(CO) 2 } 2 (μ,η 2:2 ‐EPBiPh 2 )][BArF 24 ] (E = As ( 5 ), E = Sb ( 6 )) all contain three different pnictogen atoms in a chain. To even elongate these chains, the stibenium substituted tetrahedranes 3 and [{CpMo(CO) 2 } 2 (μ,η 2:2 ‐SbPSbPh 2 )][BArF 24 ] ( 4 ) are reacted with an additional equivalent of Mo 2 PAs or Mo 2 PSb yielding novel five‐membered chains of the type E‐P‐SbPh 2 ‐P‐E′ (E = E′ = As ( 7 ); E = E′ = Sb ( 8 ); E = As, E = Sb ( 9 )), with alternating pnictogen sequences. 7 – 9 are found to be only stable in the solid state whereas a rapid equilibration with their respective starting materials 3 or 4 and Mo 2 PAs or Mo 2 PSb is observed in solution.

Permethylated Silicon: A Structural Motif with a Critical Role in Shaping the Properties of Organic–Inorganic Compounds

2025-05-27

Maria Cazacu , Madalin Damoc , Alexandru‐Constantin Stoica +2 more

Intramolecular Interactions between the Pnictogen Groups in a Rigid Ferrocene Phosphinostibine and the Corresponding Phosphine Chalcogenides, Stiboranes, and Their Complexes

2025-05-25

David Rezazgui , Jiří Schulz , Petr Štěpnička

Differences in the chemical properties of phosphorus and antimony enable the synthesis of heteroditopic derivatives whose properties can be modified by altering the pnictogen substituents. In this work, 1-(diphenylstibino)-2-(dicyclohexylphosphino)ferrocene, [Fe(η5-1-Ph2Sb-2-Cy2PC5H3)(η5-C5H5)] … Differences in the chemical properties of phosphorus and antimony enable the synthesis of heteroditopic derivatives whose properties can be modified by altering the pnictogen substituents. In this work, 1-(diphenylstibino)-2-(dicyclohexylphosphino)ferrocene, [Fe(η5-1-Ph2Sb-2-Cy2PC5H3)(η5-C5H5)] (1), and the corresponding phosphine chalcogenides [Fe(η5-1-Ph2Sb-2-Cy2P(E)C5H3)(η5-C5H5)] (E = O, S, Se) and catecholatostiboranes [Fe(η5-1-Ph2(Cl4C6O2)Sb-2-Cy2P(E)C5H3)(η5-C5H5)] (E = void, O, S, Se) were examined, with a focus on the intramolecular donor-acceptor interactions between the antimony and the phosphorus substituents. Experimental data and theoretical analysis consistently indicated that these interactions can be described as pnictogen bonding between the Lewis acidic antimony and the lone pair at the phosphorus substituent (either at the phosphorus or at the chalcogen atom) and that they are significantly stronger in the stiboranes due to the increased Lewis acidity of the Sb atom. Noncovalent interactions were also observed in the chlorogold(I) complexes obtained from 1 and catecholatostiborane [Fe(η5-1-Ph2(Cl4C6O2)Sb-2-Cy2PC5H3)(η5-C5H5)] as P-donors. As shown by experiments in Au-mediated cyclization of N-propargylbenzamide, the noncoordinated antimony group influenced the catalytic properties of the Au(I) complexes. Notably, an intramolecular Cl → Sb pnictogen bond affected the molecular geometry of the Pd(II) complex [PdCl2(1-κ2P,Sb)], which in turn suggested that the structural influence exerted by ligands of this type needs to be assessed with care.

Exploring the Reactivity of Germol Dianions with Aluminum Trichloride: Uncovering Versatile Pathways

2025-05-23

Lena Albers , Marc Schmidtmann , Thomas Müller

The reactivity analysis of dipotassiumgermoldiides K 2 [1] with aluminum trichloride in the presence of donors uncovers an unexpectedly broad range of products. The specific product formed varies, based on … The reactivity analysis of dipotassiumgermoldiides K 2 [1] with aluminum trichloride in the presence of donors uncovers an unexpectedly broad range of products. The specific product formed varies, based on the donor's characteristics, its size, and the stoichiometric ratio between the donor and the aluminium trichloride. This leads to the formation of various products, including alumole complexes of germanium 3(Do) (with Do = OEt 2 , i Pr2Me2 Im), cationic germole complexes of aluminylenes [ 14 ] + , and 2 H ‐germole derivatives such as 15a . The alumole complexes of germanium 3 are structurally best described as nido ‐type clusters or aluminagerma[5]pyramidanes. They show significant Lewis acidity and can be isolated only in the form of their donor complexes 3 ( Do ). The 2 H ‐germole derivative 15a promises a high synthetic potential due to its unprecedented germenide (R 2 C = Ge(:)‐R) group group, which is part of a butadiene system and substituted with a reactive C‐Al functionality.

Multiply Substituted (Hetero)acenes with a Phosphonate Group at the Central Unit as High‐Efficiency Light Emitters

2025-05-23

Marek Koprowski , Łucja Knopik , Ewa Różycka‐Sokołowska +4 more

A new variant of the Friedel‐Crafts‐Bradsher reaction offers access to dialkoxyphosphoryl substituted (hetero)acenes, especially to previously unavailable three‐ to seven‐substituted, tri‐ and tetracyclic compounds, and features high chemical yields up … A new variant of the Friedel‐Crafts‐Bradsher reaction offers access to dialkoxyphosphoryl substituted (hetero)acenes, especially to previously unavailable three‐ to seven‐substituted, tri‐ and tetracyclic compounds, and features high chemical yields up to 95%, excellent photoluminescence quantum yields (QY) up to 87.7%, large Stokes shifts up to 7943 cm‐1 and very mild, room temperature reaction conditions. The (RO)2P(O) has a distinct effect on the photophysical properties of acenes, increasing QYs by more than twofold compared to identical acenes, not substituted by this group. DFT and TD‐DFT calculations, combined with electron‐hole analysis, indicated that local excitation (LE) had the dominant contribution to the electron excitation mechanism, and charge transfer (CT) of about 30% provided the highest fluorescence quantum yields. Multiply substitution of (hetero)acenes bearing phosphonate moiety and electron‐diverse substituents combined with a lower number of fused aromatic rings, appear to be ideal for optimal chemical stability and high photoluminescence. The new, synthetic tool will accelerate exploitation of bulky (hetero)acene emitters for optoelectronic applications.

Synthesis and Reactivity of Triphosphaallyl Cation stabilized by N‐Heterocyclic Carbenes

2025-05-21

Julia Frötschel-Rittmeyer , Felix Hennersdorf , Jannis Fidelius +6 more

Reduction of the triphosphaallyl species 6[GaCl4] with GaI[Ga2Cl7] affords the imidazoliumyl‐substituted (L) bicyclo[2.1.1]‐triphosphane, 10[Ga2Cl7], featuring an unprecedented Ga2Cl5‐bridged P3 scaffold. Reactions of 10[Ga2Cl7] with nucleophiles (Cl‐ or NHC) result in … Reduction of the triphosphaallyl species 6[GaCl4] with GaI[Ga2Cl7] affords the imidazoliumyl‐substituted (L) bicyclo[2.1.1]‐triphosphane, 10[Ga2Cl7], featuring an unprecedented Ga2Cl5‐bridged P3 scaffold. Reactions of 10[Ga2Cl7] with nucleophiles (Cl‐ or NHC) result in rare, selective P–C bond cleavages, affording Ga2Cly‐substituted triphosphiranes (LP3Ga2Cly, y = 5, 6) via an intramolecular ring closure mechanism. Protonation of 6[GaCl4] gives rise to a similar ring closure, but without P–C bond cleavage, to afford the L2P3H+ salt 8[OTfGaCl3]2. Additionally, the palladium complex 26[GaCl4], formed through the reaction of 10[Ga2Cl7] with [Pd(PPh3)4], presents a novel bicyclic P3Pd moiety (LP3Pd(PPh3)2[GaCl4]). Comprehensive DFT calculations have been conducted to elucidate the bonding situation in 26[GaCl4], uncovering significant metal‐to‐ligand π‐back‐donation and a distinctive 3‐center‐4‐electron hyperbonding phenomenon in the P3Pd framework. These findings offer valuable insights into chemistry of cyclic polyphosphorus compounds and, in particular, the reactivity, structural flexibility, and the coordination properties of cationic triphosphorus species.

Reversible Decarbonylation of a Metal Phosphaketene

2025-05-15

Matthew J. Reveley , Joey Feld , José M. Goicoechea

We describe the synthesis of a metalated phosphastannene by reaction of the known cobalt(I) phosphaketene complex Co(DippPDI)(PCO) (DippPDI = 1,1'‐(pyridine‐2,6‐diyl)bis(N‐(2,6‐diisopropylphenyl)ethan‐1‐imine) with Sn[CH(SiMe3)2]2. The resulting compound, Co(DippPDI)(CO){P=Sn[CH(SiMe3)2]2}, contains a localized P=Sn … We describe the synthesis of a metalated phosphastannene by reaction of the known cobalt(I) phosphaketene complex Co(DippPDI)(PCO) (DippPDI = 1,1'‐(pyridine‐2,6‐diyl)bis(N‐(2,6‐diisopropylphenyl)ethan‐1‐imine) with Sn[CH(SiMe3)2]2. The resulting compound, Co(DippPDI)(CO){P=Sn[CH(SiMe3)2]2}, contains a localized P=Sn double bond, yet reacts like a phosphaketene transfer reagent, suggesting that, in solution, Co(DippPDI)(CO){P=Sn[CH(SiMe3)2]2} appears to exist in equilibrium with Co(DippPDI)(PCO) and Sn[CH(SiMe3)2]2. This is facilitated by the fact that, on decarbonylation with Sn[CH(SiMe3)2]2, the carbon monoxide extruded from the phosphaketene precursor Co(DippPDI)(PCO) remains in the coordination sphere of cobalt. The novel phosphaketene compounds (IDipp)Au(PCO) (IDipp = 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) and (DippNacNac)Zn(PCO) (DippNacnac = HC[C(Me)N(Dipp)]2; Dipp = 2,6‐iPr2C6H3) can be synthesized by reaction of Co(DippPDI)(CO){P=Sn[CH(SiMe3)2]2} with Au(IDipp)Cl or (DippNacNac)ZnCl·LiCl(OEt2)2, respectively. In the case of the former, the released stannylene Sn[CH(SiMe3)2]2 ultimately inserts into the Au–PCO bond affording the tin(IV) complex (IDipp)AuSn(PCO)[CH(SiMe3)2]2.

Diborane and Bis(boryl) Complexes of Osmium Stabilized in the Coordination Sphere of [CpOs] (Cp = η5-C5Me5)

2025-05-14

Debipada Chatterjee , Sampad Shyamal , Sundargopal Ghosh

A coherence monotone from Kirkwood-Dirac nonclassicality with respect to mutually unbiased bases

2025-05-13

Yan Liu , Zhihua Guo , Zhihao Ma +1 more

Abstract The Kirkwood-Dirac distribution, serving as an informationally complete representation of a quantum state, has recently garnered increasing attention. We investigate the Kirkwood-Dirac classicality with respect to mutually unbiased bases. … Abstract The Kirkwood-Dirac distribution, serving as an informationally complete representation of a quantum state, has recently garnered increasing attention. We investigate the Kirkwood-Dirac classicality with respect to mutually unbiased bases. For prime dimensional Hilbert spaces, {we demonstrate that a quantum state exhibits Kirkwood-Dirac classicality for two distinct sets of mutually unbiased bases $(A,B)$ and $(A,B')$ if and only if it is incoherent with respect to $A$}. We subsequently introduce a coherence monotone based on Kirkwood-Dirac nonclassicality with respect to mutually unbiased bases. Additionally, we establish that this coherence monotone can be expressed through weak values, suggesting that quantum coherence can be utilized to detect anomalous weak values.&#xD;

Structural Analysis of Artin’s Cokernel for the Group (Q2l×C7)

2025-05-09

Salah Hassoun Jihadi

A fractional Abelian group is a mathematical structure in which operations—typically involving fractions or concepts from fractional calculus—are defined within the context of an Abelian group. In this study, we … A fractional Abelian group is a mathematical structure in which operations—typically involving fractions or concepts from fractional calculus—are defined within the context of an Abelian group. In this study, we determine the cyclic decomposition of the fractional Abelian group AC(Q2l×C7). Here, group(Q2l×C7) is the direct product group of the quaternion group Q2l of order 4l and the cyclic group C7 of order 7, then the order of The group(Q2l×C7) is 28l. After knowing Ar(Q2l×C7), the result was as follows: $$A C\left(Q_{2 l}\times C_7\right)=\stackrel{4}{\bigoplus}_{i=1}C_2.$$ The results offer deeper insight into the structural characteristics of the group (Q2l×C7), with meaningful implications for both representation theory and computational algebra. Through the analysis of matrix transformations and invariant factor decomposition, this study contributes to a broader understanding of group theory and its applications in mathematical and theoretical contexts. Moreover, the findings may provide a foundational basis for future research in areas such as character theory and modular representations within abstract algebra.

Part III

2025-05-08

Lewis acidity of the SbCl3/o‐chloranil system

2025-05-08

Nathanael H. Hunter , Ferit Şit , Logan T. Maltz +1 more

While SbCl3 is typically inert toward oxidation by ortho‐quinones, we use o‐chloranil to show that the outcome of such reactions may be altered by the presence of a donor such … While SbCl3 is typically inert toward oxidation by ortho‐quinones, we use o‐chloranil to show that the outcome of such reactions may be altered by the presence of a donor such as triphenylphosphine oxide, which readily traps the SbCl3(catCl) synthon (catCl = tetrachlorocatecholate) in the form of the corresponding adduct Ph3PO→SbCl3(catCl). The same reaction in the presence of a chloride salt affords the corresponding antimonate anion [Cl4Sb(catCl)]‐. Computational studies indicate that the putative SbCl3(catCl) synthon has a higher chloride ion affinity than SbCl5, suggesting significant Lewis acidity. This property is further demonstrated by the use of the SbCl3/o‐chloranil system for both THF polymerization and Friedel‐Crafts‐type alkylation of benzene using 1‐fluorooctane. Finally, the reaction of E‐stilbene with o‐chloranil in the presence of SbCl3 affords the corresponding benzodioxene, suggesting that SbCl3 may also operate as a redox‐active catalyst.

Cyclopentadienyl coordinated cationic compounds of group 14 important in catalysis

2025-05-06

Kinga Piorecka

Cyclic (Alkyl)(amino)silylene Aluminum(III) Iodide Complex and Its Nucleophile Dependent Reactivities

2025-05-05

Taichi Koike , Akari Sato , Naoki Sakurata +1 more

Dual Optical and Biological Functionalities of the Bismuth-Based Metal Halide Semiconductor (C8H12N)4Bi2Cl10

2025-05-01

Chaima Jridi , Sameh Sellami , Nour Elleuch +2 more

Corrigendum to “Exploring the chemistry of divalent P(I) compounds: an insight from theory” [Polyhedron 276 (2025) 117561]

2025-05-01

Bijoy Ghosh , Sanchaita Rajkhowa , Bitupon Borthakur

Multi‐talented Bismuthinidenes: Double C(sp3)‐I Bond Activation Using Single or Two Bi Centers.

2025-04-30

Pavel Novák , Martin Hejda , Roman Jambor +3 more

The reaction of [2,6‐(DippN=CH)2C6H3]Bi (1Dipp, Dipp = 2,6‐iPrC6H3) with CH2I2 proceeded via double C‐I bond activation yielding [2,6‐(DippN=CH)2C6H3]Bi(μ‐(Bi,N)‐CH2)I2 (3). By contrast, the reaction of 1Dipp with 1,2‐diiodoethane provided [2,6‐(DippN=CH)2C6H3]BiI2 (1DippI2) … The reaction of [2,6‐(DippN=CH)2C6H3]Bi (1Dipp, Dipp = 2,6‐iPrC6H3) with CH2I2 proceeded via double C‐I bond activation yielding [2,6‐(DippN=CH)2C6H3]Bi(μ‐(Bi,N)‐CH2)I2 (3). By contrast, the reaction of 1Dipp with 1,2‐diiodoethane provided [2,6‐(DippN=CH)2C6H3]BiI2 (1DippI2) and ethene. The tert‐butyl analogue [2,6‐(tBuN=CH)2C6H3]Bi (1tBu) reacted with CH2ClX to give [2,6‐(tBuN=CH)2C6H3]Bi(CH2Cl)X (X = I (4) or Cl (5)). Further, its reactivity with CH2I2 was sensitive towards the stoichiometry since using a 1:1 ratio gave a mixture of dinuclear complex {[2,6‐(tBuN=CH)2C6H3]Bi(I)}2(μ‐(Bi,Bi)‐CH2) (6) and [2,6‐(tBuN=CH)2C6H3]Bi(CH2I)I (7). The reaction could be shifted in favor of 7 using an excess of CH2I2, but with 0.45 eq. of CH2I2 compound 6, as a product of double C‐I bond activation mediated by two Bi atoms was isolated as the main product.

(Trialkylsilyl)germanes (tBuMeRSi)GeH3 (R = Me, tBu)

2025-04-30

Philipp Schmid , Karin Bartl , Robert Saf +3 more

Phosphanyl‐Substituted Tetrylenes and Ditetrelenes – Impact of Steric Bulk on Tetrylene/Ditetrelene Stability

2025-04-30

Keith Izod , Ahmed Hadadi , Mo Liu +4 more

Phosphorus‐substituted tetrylenes and ditetrelenes remain something of a rarity. The reaction between SnCl2 and two equivalents of (Dep2P)Li at low temperature gave the bis(phosphanyl)stannylene {(Dep)2P}2Sn (4Sn), although this compound decomposes … Phosphorus‐substituted tetrylenes and ditetrelenes remain something of a rarity. The reaction between SnCl2 and two equivalents of (Dep2P)Li at low temperature gave the bis(phosphanyl)stannylene {(Dep)2P}2Sn (4Sn), although this compound decomposes in solution at room temperature (Dep = 2,6‐Et2C6H3). Compound 4Sn is monomeric in the solid state and exhibits significant Sn…Ar contacts, which mitigate the electron‐deficiency of the Sn centre. In contrast, the reaction between GeCl2(1,4‐dioxane) and two equivalents of (Tep2P)Li gave the digermene (Tep2P)2Ge=Ge(PTep2)2 (5Ge; Tep = 2,4,6‐Et3C6H2). Compound 5Ge crystallises as a strongly trans‐bent and twisted digermene; however, in solution, variable‐temperature 31P{1H} and 1H DOSY NMR spectroscopy reveal a dynamic equilibrium between the germylene and digermene forms of 5Ge.

Synthesis of Molecular Organo‐f‐Element‐Polyphosphides with Non‐Classical Divalent Lanthanide Precursors

2025-04-29

David N. Frick , E. Pross , Ralf Köppe +1 more

The coordination and functionalization of white phosphorus (P4) by transition metal and main group element compounds has led to a great variety of polyphosphides. However, larger polyphosphides of the rare‐earth … The coordination and functionalization of white phosphorus (P4) by transition metal and main group element compounds has led to a great variety of polyphosphides. However, larger polyphosphides of the rare‐earth elements are elusive. In this study, we report the synthesis and full characterization of the largest polyphosphides of the f‐elements, [K(18‐crown‐6)]2[(Cp′′2Ln)2(µ4‐ƞ2:ƞ2:ƞ2:ƞ2‐P14)], which was isolated along with [K(18‐crown‐6)][(Cp′′2Ln)2(µ‐ƞ3:ƞ3‐P3)] (Ln = La, Ce, Cp′′ = 1,3‐bis(trimethylsilyl)cyclopentadienyl). These compounds were obtained by using non‐classical divalent compounds of the early lanthanides for the reduction of white phosphorus.

Synthesis of Molecular Organo‐f‐Element‐Polyphosphides with Non‐Classical Divalent Lanthanide Precursors

2025-04-29

David N. Frick , E. Pross , Ralf Köppe +1 more

Synthesis and optical properties of 1,2-diphospholes

2025-04-28

I. F. Sakhapov , Zufar N. Gafurov , Dmitry G. Yakhvarov

Insights into the Factors Controlling the Origin of Activation Barriers in the [2 + 2] Cycloaddition Reactions of Heavy Imine-like Molecules Featuring a Ge=Group 15 Double Bond with Heterocumulenes

2025-04-25

Zhengfeng Zhang , Ming‐Der Su

The [2 + 2] cycloaddition reactions of the heterocumulene (N=C=N) with the heavy imine-like molecule Ge=G15-Rea (G15 = Group 15 element) were examined using density functional theory (M06-2X-D3/def2-TZVP). The theoretical … The [2 + 2] cycloaddition reactions of the heterocumulene (N=C=N) with the heavy imine-like molecule Ge=G15-Rea (G15 = Group 15 element) were examined using density functional theory (M06-2X-D3/def2-TZVP). The theoretical findings indicate that the doubly bonded Ge=G15 moiety in Ge=G15-Rea (L1L2Ge=G15L3) is characterized by electron-sharing bonding between the triplet L1L2Ge and triplet G15–L3 fragments. All five Ge=G15-based heavy imine analogues readily undergo [2 + 2] cycloaddition reactions with N=C=N. Energy decomposition analysis (EDA–NOCV) suggests that the [2 + 2] cycloaddition reaction between Ge=G15-Rea and N=C=N involves a donor–acceptor (singlet–singlet) interaction instead of an electron-sharing (triplet–triplet) interaction. Frontier molecular orbital (FMO) theory and the energy decomposition analysis–natural orbitals for chemical valence (EDA–NOCV) findings emphasize that the key bonding interaction involves the occupied p-π orbital of Ge=G15-Rea and the vacant p-π* orbital of C=N=C. Based on the activation strain model results, the activation barrier of the [2 + 2] cycloaddition reaction is predominantly controlled by the deformation energies of Ge=G15-Rea and N=C=N.

A Novel Perchlorinated Cyclohexasilane Salt with Intramolecular Hydrogen Bonding and Its Application in the Synthesis of Cyclohexasilane

2025-04-24

Zhikun Liu , Xuefei Yang , Ping Chen

Ionic compounds of tetradecachlorocyclohexasilane, a critical precursor for cyclohexasilane and its derivatives, have been synthesized using various methods. However, these approaches are often hindered by low yields, high costs, and … Ionic compounds of tetradecachlorocyclohexasilane, a critical precursor for cyclohexasilane and its derivatives, have been synthesized using various methods. However, these approaches are often hindered by low yields, high costs, and environmental concerns. In this study, a novel perchlorinated cyclohexasilane salt, [(i-Pr2EtNH)2Cl+]2[Si6Cl14 2-], was synthesized by the cyclization of trichlorohydrosilanes with diisopropylethylamine. The compound differs from previously reported six-membered silicocyclic ionic compounds. Notably, the chlorine atom in the cation does not form a direct covalent bond with the surrounding atoms. Instead, it forms a hydrogen bond, a feature not observed in the cationic components of other tetradecachlorocyclohexasilane dianion compounds. The structure was confirmed through single-crystal X-ray diffraction, NMR spectroscopy, and elemental analysis. The perchlorinated cyclohexasilane salt was subsequently reduced to cyclohexasilane using metal hydrides, achieving an overall yield of 44.2% across the two-step process. This method offers several advantages, including cost-effectiveness, high yields, simple purification, and mild reaction conditions. The results demonstrate the utility of this approach for synthesizing cyclohexasilane and advancing its applications as feedstocks for silicon deposition in the development of micro- and nano-silicon materials.

Polyphosphorus Ligand Complexes of Coinage Metals for Multiple Capturing of Intact P4 Tetrahedra

2025-04-22

Claudia Goeschl , Eugenia V. Peresypkina , Barbara Hiltl +3 more

Two‐ and three‐component self‐assembly reactions of [CpRFe(η5‑P5)] (CpR = C5(CH3)5 (Cp*, 1a), C5(4‑EtC6H4)5) (CpPEt, 1b)) with the coinage metal salts [Cu(CH3CN)4][SbF6] or AgSbF6 were investigated to study the prerequisites for … Two‐ and three‐component self‐assembly reactions of [CpRFe(η5‑P5)] (CpR = C5(CH3)5 (Cp*, 1a), C5(4‑EtC6H4)5) (CpPEt, 1b)) with the coinage metal salts [Cu(CH3CN)4][SbF6] or AgSbF6 were investigated to study the prerequisites for the potential coordination of white phosphorus by using a sterically encumbered CpR ligand and non‐coordinating anions. In the self‐assembly reactions with white phosphorus, either 0D or 1D coordination complexes are formed, all of which feature coordinated intact P4 tetrahedra and thus comprise an unprecedented class of mixed polyphosphorus ligand complexes capable of complete release of P4 in solution confirmed by NMR studies. The bulkiness of the used CpR ligand and the correctly chosen solvent allowed for obtaining more beneficial structural motifs, the first discrete tetra‐ and penta‐coordinated cyclo‐P5 ligand complexes, that provide the maximal content of coordinated P4 molecules per species known so far. All products are characterized by single‐crystal X‐ray diffraction, NMR spectroscopy, and mass spectrometry.

A Stibenium Stabilized by Intramolecular Coordination from a Phosphine

2025-04-21

Shuhei Kawamoto , Koichiro Masada , Takahiro Sasamori

Abstract A bis(ferrocenyl)stibenium with intramolecular phosphine coordination was obtained as an air‐stable compound after abstracting bromide from the corresponding bromostibine. UV–vis spectroscopy measurements and DFT calculations revealed that this stibenium … Abstract A bis(ferrocenyl)stibenium with intramolecular phosphine coordination was obtained as an air‐stable compound after abstracting bromide from the corresponding bromostibine. UV–vis spectroscopy measurements and DFT calculations revealed that this stibenium exhibits ligand‐to‐metal charge‐transfer absorption bands that arise from the electron transfer from the ferrocenyl moieties to the Sb center, suggesting high electrophilicity for the latter. The redox behavior of the isolated stibenium was investigated by cyclic‐voltammetry measurements, which revealed irreversible oxidation behavior.