Two SiSi Double Bonds Connected by a Phenylene Bridge

Bejan, Iulia; Scheschkewitz, David

doi:10.1002/anie.200701744

Cited by 116 publications

(61 citation statements)

References 45 publications

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“…Calculations for 12 have demonstrated that the LUMO level is lowered [-1.552 (5a) and -2.108 (12) eV], thus keeping the HOMO levels nearly constant [-5.141 (5a) and -5.137 (12) eV], in agreement with the orbital shapes for 5a and the previously mentioned electrochemical experimental results. The significant 3n-2p p conjugation are also found in the HOMO-2 and HOMO-3 of 12.…”

Section: Theoretical Studies Of P-conjugated Phosphasilenessupporting

confidence: 84%

“…The calculated wavelengths of 364 (5a) and 456 (12) nm are comparable to the observed values. The absorption at 364 nm of 5a is assignable to the mixed version of the HOMO!LUMO (p-p*) and HOMO-1!LUMO ((n + p of Eind benzene)-p*) transitions with almost equal weighting.…”

Section: Theoretical Studies Of P-conjugated Phosphasilenessupporting

confidence: 83%

“…2 and 3. The aryl and the arylene groups are entirely coplanar with the Si=P double bond(s), having the P-Si-C-C torsion angles of 3.04(13) (5a), 1.1(4) (5b), 2.0(2) (5c), and 0.8(2)8 (12), respectively, which is well suited for the 2p p -3p p conjugation. This coplanarity is apparently attained by the rigid Eind groups, oriented trans and perpendicular with respect to the Si=P bond, as observed in the disilene case [13].…”

Section: X-ray Structural Aspectsmentioning

confidence: 98%

“…[12] and we [13] independently reported the synthesis and characterization of the disilene analogues of the oligo(pphenylenevinylene)s (Si-OPVs) (Scheme 1). In our case, the newly developed fused-ring bulky 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl groups, abbreviated as ''Eind'' groups (''E'' for ethyl), effectively protect the reactive Si=Si fragments, thus providing the highly coplanar arrangement of the Si-OPV dimer framework.…”

Section: Introductionmentioning

confidence: 97%

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π-conjugated phosphasilenes stabilized by fused-ring bulky “Rind” groups

Matsuo

Tamao

2010

Comptes Rendus. Chimie

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Section: Theoretical Studies Of P-conjugated Phosphasilenessupporting

confidence: 84%

Section: Theoretical Studies Of P-conjugated Phosphasilenessupporting

confidence: 83%

Section: X-ray Structural Aspectsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 97%

See 2 more Smart Citations

π-conjugated phosphasilenes stabilized by fused-ring bulky “Rind” groups

Matsuo

Tamao

2010

Comptes Rendus. Chimie

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“…Especially Scheschkewitz and Tamao should be mentioned in this context, as they independently reported the synthesis of various π conjugated systems containing Si Si units. 11,12 Their disilenes consist of extended π conjugated systems with bridged and terminal phenylene or phenyl groups, exhibiting particularly interesting photochemical properties. Wishing to combine the remarkable developments in the eld of extended π electron systems containing heavier main group elements and d π electron systems, lead us to investigate the chemistry of a new type of d π electron systems with a π electron spacer of heavier main group elements.…”

Section: Introductionmentioning

confidence: 99%

The Synthesis and Properties of Bimetallic d-^|^pi; Electron Systems Containing Metallocenyl Substituents of Fe or Ru, and ^|^pi;-Electron Spacers of Heavier Main Group Elements from Group 14 or 15

Sasamori

2014

J. Synth. Org. Chem. Jpn.

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Abstract:Relative to π electron systems between elements from the second row of the periodic table, those between heavier main group elements should exhibit higher HOMO and lower LUMO levels. Moreover, such π electron systems between heavier main group elements are expected to be good electron acceptors and donors, and they should also exhibit good electron transporting properties. With the ultimate goal to create unprecedented π electron systems between heavier main group elements in mind, we designed d π electron systems containing heavier main group elements in the π electron moiety and transition metals in the d electron moiety. In this account article, we present our recent progress on the generation of bimetallic ferrocenyl and ruthenocenyl based d π electron systems containing π bond spacers of heavier main group elements from group 14 or 15.

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Heavy Analogs of Alkenes, 1,3‐Dienes, Allenes and Alkynes: Multiply Bonded Derivatives of Si, Ge, Sn and Pb

Lee

Sekiguchi

2010

Organometallic Compounds of Low‐Coordinate Si, Ge, Sn and Pb

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Unsaturated hydrocarbons, alkenes, alkynes and dienes are among the most fundamental classes of organic compounds. The great variety and richness of organic chemistry are to a large extent caused by the disposition of carbon to form highly reactive carbon-carbon and carbon-heteroatom multiple bonds. Standard textbooks on organic chemistry describe the C=C double bond as one made of a σ -bond, formed by the linear end-on overlap of sp 2 -hybrid orbitals of each carbon partner (sp 2 -sp 2 interaction), and a π -bond, formed by the side-on overlap of unhybridized 2p-orbitals (2p π -2p π interaction). Analogously, the carbon-carbon triple bond consists of a σ -bond, formed by the linear end-on overlap of the two sp-hybrids (sp-sp interaction), and two mutually orthogonal π -bonds, each formed by the side-on overlap of unhybridized 2p-orbitals (2p π -2p π interaction). Because the s-character of the hybrid orbitals used for the formation of carbon-carbon bonds progressively increases from the single (sp 3 -sp 3 ) to the double (sp 2 -sp 2 ) and triple (sp-sp) bonds, C=C double bonds are shorter (and stronger) than C-C single bonds, and C≡C triple bonds are shorter (and stronger) than C=C double bonds. In accord with their hybridization types, the geometry of the carbon-carbon double bond in alkenes R 2 C=CR 2 is planar with an idealized R-C=C bond angle of 120 • , and the geometry of the carbon-carbon triple bond in alkynes R-C≡C-R is linear with an idealized R-C≡C bond angle of 180 • .The structures and bonding of the alkene analogs of heavy group 14 elements, both in the crystalline form and in solution, are sharply distinctive from those of their organic counterparts (alkenes); therefore, before proceeding to the discussion on each class of heavy alkenes we will briefly comment on the specific structural features of the title compounds. Structure and bondingIn contrast to organic alkenes, which are typically planar and feature diagnostically short double bonds (av. 1.34Å for >C=C< vs av. 1.54Å for >C-C<), their analogs of the heavy group 14 elements >E=E< (E = Si-Pb) revealed diverse types of structural modes sharply distinctive from those of their organic counterparts. Thus, apart from the stretching of the E=E bond descending group 14, there are two fundamental structural deformations characteristic of heavy alkenes >E=E< and leading to their departure from planarity: trans-bending at E centers and twisting about the E=E bond. The peculiar trans-bending geometry, resulting in the overall pyramidalization at the heavy group 14 elements, was rationalized in the framework of two different MO models providing alternative explanations for this phenomenon. 5 The first qualitative model considered formation of the double bond as a result of the interaction of two monomeric carbene units, taking into account the different groundstate multiplicities of carbenes and their heavy analogs. Thus, interaction of the two monomeric carbenes, which typically have triplet ground states (or alternatively, singlet ground states with ...

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Two SiSi Double Bonds Connected by a Phenylene Bridge

Abstract: Electronic communication between two SiSi double bonds is enabled by a phenylene linkage and expressed in a large red shift of the longest‐wavelength UV/Vis absorptions of deep red tetrasiladiene 1 compared to yellow phenyldisilene 2.

Cited by 116 publications

References 45 publications

π-conjugated phosphasilenes stabilized by fused-ring bulky “Rind” groups

π-conjugated phosphasilenes stabilized by fused-ring bulky “Rind” groups

The Synthesis and Properties of Bimetallic d-^|^pi; Electron Systems Containing Metallocenyl Substituents of Fe or Ru, and ^|^pi;-Electron Spacers of Heavier Main Group Elements from Group 14 or 15

Heavy Analogs of Alkenes, 1,3‐Dienes, Allenes and Alkynes: Multiply Bonded Derivatives of Si, Ge, Sn and Pb

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