Isolable silylenes and their diverse reactivity

Wang, Liliang; Li, Yinhuan; Li, Zhifang; Kira, Mitsuo

doi:10.1016/j.ccr.2022.214413

Cited by 41 publications

(38 citation statements)

References 182 publications

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“…S13, ESI †) is observed at a longer wavelength than that of 1a (l max = 440 nm). 40,42 The HOMO-LUMO gap of 3b (3.68 eV) is also narrower than that of free germylene 1b (5.94 eV), which is consistent with the red-shifted absorption maximum [3b À : l max = 590 nm (Fig. S13, ESI †), 1b: l max = 450 nm].…”

supporting

confidence: 72%

Trinuclear anionic gold clusters bridged by dialkylsilylene and dialkylgermylene

Zhen

Huang

et al. 2022

Chem. Commun.

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supporting

confidence: 72%

Trinuclear anionic gold clusters bridged by dialkylsilylene and dialkylgermylene

Zhen

Huang

et al. 2022

Chem. Commun.

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“…, Cp* 2 Si:) was reported by Jutzi only in 1986 . Since then, a plethora of highly reactive silylenes has been prepared . Unlike carbenes, which can exist in the singlet or triplet ground state (depending on substituents), silylenes are generally closed shell, having a lone pair and vacant p-orbital, ,,, Thus, despite the high propensity of silylenes for small molecule activation, ,, examples of silylene insertion into the aromatic C–C bonds are rare.…”

Section: Introductionmentioning

confidence: 99%

Room Temperature Intermolecular Dearomatization of Arenes by an Acyclic Iminosilylene

et al. 2023

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A novel nontransient acyclic iminosilylene (1), bearing a bulky super silyl group (−Si t Bu 3 ) and N-heterocyclic imine ligand with a methylated backbone, was prepared and isolated. The methylated backbone is the feature of 1 that distinguishes it from the previously reported nonisolable iminosilylenes, as it prevents the intramolecular silylene center insertion into an aromatic C−C bond of an aryl substituent. Instead, 1 exhibits an intermolecular Buchner-ring-expansion-type reactivity; the silylene is capable of dearomatization of benzene and its derivatives, giving the corresponding silicon analogs of cycloheptatrienes, i.e. silepins, featuring seven-membered SiC 6 rings with nearly planar geometry. The ring expansion reactions of 1 with benzene and 1,4bis(trifluoromethyl)benzene are reversible. Similar reactions of 1 with N-heteroarenes (pyridine and DMAP) proceed more rapidly and irreversibly forming the corresponding azasilepins, also with nearly planar seven-membered SiNC 5 rings. DFT calculations reveal an ambiphilic nature of 1 that allows the intermolecular aromatic C−C bond insertion to occur. Additional computational studies, which elucidate the inherent reactivity of 1, the role of the substituent effect, and reaction mechanisms behind the ring expansion transformations, are presented.

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“…J HSi = 6.7, 4 J HP = 2.2, 2H, NH 2 ), 1.46 (d, 2 J HP = 4.4, 6H, CH 3 ), 1.44 (d, 2 J HP = 4.4, 6H, CH 3 ), 0.49 (s, 54H, TMS). 29…”

Section: * Sı Supporting Informationmentioning

confidence: 99%

“…In the field of low valent silicon chemistry, a variety of silylene species has been reported in the literature. − On the quest for main group compounds that exhibit transition-metal-like behavior regarding the activation of small molecules or even the catalytic activity, the design of the ligand is key. Thereby, the steric and electronic properties of the silylenes can be tuned as well as the HOMO and LUMO orbitals of the molecule which mimic frontier orbitals of transition metals .…”

Section: Introductionmentioning

confidence: 99%

Steric and Electronic Properties of Phosphinimide-Based Silylenes─The Influence of the Phosphine Moiety

et al. 2022

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In the present study, we investigated the steric and electronic properties of differently substituted phosphinimide-based silylenes. PMe2Ph, PPh3, and P(tBu)3 were chosen as starting materials and the corresponding siliranes were synthesized as “masked” silylenes. In order to compare the silylenes, iron–carbonyl complexes of these of the type Fe(CO)4L were analyzed regarding their CO vibrations via IR spectroscopy. Furthermore, kinetic experiments of the activation reaction of NH3 were conducted with the siliranes and density functional theory calculations of the HOMO and LUMO energy levels were performed for the free silylenes. It could be shown that the steric and electronic properties of phosphinimide-substituted silylenes can be effectively tuned through the modification of the phosphine moiety of the ligand. In addition, the trends observed for the silylenes are in good agreement with the trends shown in the “steric and electronic map” from C. A. Tolman for the utilized phosphines. This implies that the properties of further phosphinimide-based silylenes can be estimated with the help of Tolman’s map which could serve as a guide for future ligand design.

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Isolable silylenes and their diverse reactivity

Cited by 41 publications

References 182 publications

Trinuclear anionic gold clusters bridged by dialkylsilylene and dialkylgermylene

Trinuclear anionic gold clusters bridged by dialkylsilylene and dialkylgermylene

Room Temperature Intermolecular Dearomatization of Arenes by an Acyclic Iminosilylene

Steric and Electronic Properties of Phosphinimide-Based Silylenes─The Influence of the Phosphine Moiety

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