Mono-and bimetallic zwitterionic chromium(0) and tungsten(0) allenyls

Elena A. Giner, Alicia Santiago, Mar Gómez-Gallego, Carmen Ramírez De Arellano, Rebecca C. Poulten, Michael K. Whittlesey, Miguel A. Sierra

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12 Citations (Scopus)

Abstract

A series of stable chiral (racemic), formally neutral, zwitterionic mono- and bimetallic M(CO5[C(OEt)=C=CR(NHC)] (M = Cr, W) σ-allenyls are ready available by the addition of N-heterocyclic carbenes (NHCs) to Cr(0) and W(0) alkynyl Fischer carbene complexes. Different classes of NHCs, (e.g., 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene, and their six- and seven-membered analogues and 1,3-bis(dimethyl)imidazol-2-ylidene) were employed as nucleophiles in these C-C bond-forming reactions yielding the novel complexes in essentially quantitative yields. A systematic experimental and computational study of the electronic properties of the Cr- and W-allenyls shows that their UV-vis spectra are directly influenced by the structure of the heterocyclic moiety derived from the NHC (ring size, substituents on the N atoms) and by the nature of the metal fragment (Cr/W). The electron-releasing nature of these complexes allows them to participate in electron-transfer reactions in the ground state, leading to a type of charged α,β-unsaturated Fischer carbenes that incorporate an NHC fragment in their structure.

Original languageEnglish
Pages (from-to)5450-5461
Number of pages12
JournalInorganic Chemistry
Volume54
Issue number11
DOIs
Publication statusPublished - 1 Jun 2015

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    Giner, E. A., Santiago, A., Gómez-Gallego, M., Ramírez De Arellano, C., Poulten, R. C., Whittlesey, M. K., & Sierra, M. A. (2015). Mono-and bimetallic zwitterionic chromium(0) and tungsten(0) allenyls. Inorganic Chemistry, 54(11), 5450-5461. https://doi.org/10.1021/acs.inorgchem.5b00492