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- Title
Formation and Redox Interconversion of Niobium Methylidene and Methylidyne Complexes.
- Authors
Searles, Keith; Smith, Kyle T.; Kurogi, Takashi; Chen, Chun ‐ Hsing; Carroll, Patrick J.; Mindiola, Daniel J.
- Abstract
The niobium methylidene [{(Ar′O)2Nb}2(μ2-Cl)2(μ2-CH2)] ( 2) can be cleanly prepared via thermolysis or photolysis of [(Ar′O)2Nb(CH3)2Cl] ( 1) (OAr′=2,6-bis(diphenylmethyl)-4-tert-butylphenoxide). Reduction of 2 with two equivalents of KC8 results in formation of the first niobium methylidyne [K][{(Ar′O)2Nb}2(μ2-CH)(μ2-H)(μ2-Cl)] ( 3) via a binuclear α-hydrogen elimination. Oxidation of 3 with two equiv of ClCPh3 reforms 2. In addition to solid state X-ray analysis, all these complexes were elucidated via multinuclear NMR experiments and isotopic labelling studies, including a crossover experiment, support the notion for a radical mechanism as well as a binuclear α-hydrogen abstraction pathway being operative in the formation of 2 from 1.
- Subjects
OXIDATION-reduction reaction; NIOBIUM compounds; CARBYNES; METAL complexes; PHOTOLYSIS (Chemistry); THERMOLYSIS; NUCLEAR magnetic resonance
- Publication
Angewandte Chemie, 2016, Vol 128, Issue 23, p6754
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201511867