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Generation,bonding and reactivity of transient zinc-substituted silylenes

Science China Chemistry 2024年第4期67卷 1256-1262页

作者： Cheng Xu Thayalan Rajeshkumar Laurent Maron Xuebing Leng Yaofeng Chen State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic ChemistryUniversity of Chinese Academy of SciencesChinese Academy of SciencesShanghai 200032China Spin-X Institute School of Chemistry and Chemical EngineeringState Key Laboratory of Luminescent Materials and DevicesGuangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional MaterialsSouth China University of TechnologyGuangzhou 510641China LPCNO CNRS&INSAUniversitéPaul SabatierToulous 31077France

The metal-substituted silylenes are of high interest,as the theoretical studies indicated that the silylenes with electropositive substituents have a small ΔE_(S-T)(singlet-triplet energy gap)or even the ground-state triplets.However,such compounds are highly unstable,and only two transient alkali metal-substituted silylenes M(^(t)Bu_(3)Si)Si:(M=Li,K)were generated by photoextrusion of the alkali metal-substituted silacyclopropenes and merely studied by spectroscopic method(EPR)at low temperature(14 to 50 K).Herein,we report the generation of transient zinc-substituted silylenes from zinc silacyclopropanyl complexes under very mild and convenient conditions.The generated transient zinc-substituted silylenes are highly reactive and undergo intermolecular cycloaddition with alkenes for the synthesis of zinc-substituted Si-heterocyclic compounds.If there is no substrate,the zinc-substituted silylenes attack the C-C bonds of the β-diketiminato ligands and break the C-C bonds.DFT studies further highlight the silylene nature of the zinc-substituted silylene and a very small ΔE_(S-T)(4.4 kcal/mol).

关键词： zinc complex silylene C-C bond cleavage cycloaddition DFT calculations

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Recent advances on carborane-based ligands in low-valent group 13 and group 14 elements chemistry

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Chinese Chemical Letters 2022年第8期33卷 3672-3680页

作者： Hao Wang School of Chemistry and Chemical Engineering Southeast UniversityNanjing 211189China

Carboranes are a class of polyhedral boron-carbon molecular clusters,they can serve as versatile ligands in stabilizing low-valent main group element compounds,due to their exceptionally thermal and chemical stabilities,easy modifications at the cage carbon vertices,as well as large spherical steric effects.These carborane-based ligands provide interesting opportunities for the synthesis of low-valent main group element compounds with novel structure and reactivity,which indeed enrich the chemistry of low-valent element main group compounds.This review summarizes the recent advances in the chemistry of lowvalent group 13 and group 14 element compounds supported by carborane-based ligands.Achievements and perspectives in this new and flourishing field are discussed in this review.

关键词： Carborane Borylene Carbene silylene Main group chemistry

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Forging a Cage into a Chain:Stepwise Transformation of P_(4) by silylenes to a Si_(3)P_(4) Motif

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CCS Chemistry 2022年第6期4卷 1843-1849页

作者： Xiaofei Sun Alexander Hinz Peter W.Roesky Institute of Inorganic Chemistry Karlsruhe Institute of Technology(KIT)76131 Karlsruhe

We have discovered a route to access the longest low-valent molecular silaphospha-chain,a sevenmembered chain structure that incorporates three silicon and four phosphorus atoms by stepwise activation of white phosphorus(P_(4))using two different silylene precursors.The chain species was formed via a highly reactive polyphosphide intermediate.The isolation of a stable analogue of this reaction intermediate was achieved by stepwise reaction with mono and bis(silylenes).Due to the rigidity of the ferrocenediyl framework of the bis(silylene),the isomerization process of the chain structure was hampered.Theoretical studies such as natural bond orbital and atoms in molecules analyses of the seven-membered chain species indicated some degree of delocalization of the double bond system.

关键词： phosphorus P_(4)activation silylene silicon main group synthesis

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Synthesis of a Mixed silylene–Carbene Chelate Ligand from an N-Heterocyclic Silylcarbene Mediated by Nickel

Synthesis of a Mixed Silylene–Carbene Chelate Ligand from a...

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中国化学会第九届全国无机化学学术会议

作者： Gengwen Tan Matthias Driess Xinping Wang Department of Chemistry Nanjing University Department of Chemistry Technische Universitt Berlin

N-heterocyclic carbenes（NHCs） represent one of the most widely utilized supporting ligands in transition metal（TM） chemistry in the last decades.[1] These complexes have exhibited numerous superior activities in comparison to phosphine complexes owing to the stronger σ donor ability of NHC ligands.[2] Whereas, the heavy homologs of NHCs, the N-heterocyclic silylenes（NHSis） are emerging as a novel class of versatile steering ligands in the coordination chemistry of the transition metals, and their complexes have already shown remarkable features in small molecule activation and as precatalysts for various types of organic transformations.[3] Therefore, combining these two ligand types in one chelate molecule might enable new coordination features at TMs. Moreover, the presence of both strong σ-donating moieties might facilitate the coordination and dissociation of other ligands thereby improving the reactivity or catalytic performance of respective TM complexes.Herein I present the unexpectedly facile formation of the first mixed NHSi-NHC chelate complex[L1Si:（CH2）（NHC）]NiBr2 2 [L1 = CH（Me C=NAr）2, Ar = 2,6-iP r2C6H3;NHC =3,4,5-trimethylimidazol-2-yliden-6-yl] through the hydrogen atom migration from the silicon atom to the exocyclic methylene group in L2Si（H）（CH2）NHC [L2 = CH（C=CH2）（CMe）（NAr）2, Ar = 2,6-iPr2C6H3;NHC =3,4,5-trimethylimidazol-2-yliden-6-yl] mediated by Ni Br2. The analogous reduction of 2 in the presence of1,2-bis（dimethylphosphino）ethane（DMPE） furnishes the first mixed NHSi-NHC（DMPE）Ni0 complex 3. Moreover,complex 2 shows a high catalytic activity for Kumada-Corriu-type cross-coupling reactions.[4]

关键词： silylene main group chemistry N-heterocyclic carbene homogeneous catalysis cross-coupling reaction

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