Buschmann Dennis A, Schumacher Lion, Anwander Reiner
Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany.
Chem Commun (Camb). 2022 Aug 11;58(65):9132-9135. doi: 10.1039/d2cc03532d.
Complexes CpLn(μ-CH)(μ-CH)(μ-H)(thf) (Ln = Y, Dy; Cp = CMe) are formed elimination of CH and CH from the respective trinuclear polymethyl complexes [CpLn(μ-CH)], involving the methyl/methylidene complex CpLn(μ-CH)(μ-CH)(μ-CH)(thf) as an intermediate. Compound CpY(μ-CH)(μ-CH)(μ-H)(thf) displays "Schrock-type" nucleophilic carbene reactivity, converting ketones into the corresponding terminal alkenes. Treatment of CpY(μ-CH)(μ-CH)(μ-H)(thf) with [D]methanol proved accessibility of all small-group functionalities as indicated by the simultaneous formation of deuterated HD and deuterated methanes CHD and CHD.
通过从相应的三核多甲基配合物[CpLn(μ-CH)]中消除CH和CH形成配合物CpLn(μ-CH)(μ-CH)(μ-H)(thf)（Ln = Y，Dy；Cp* = CMe），其中甲基/亚甲基配合物CpLn(μ-CH)(μ-CH)(μ-CH)(thf)作为中间体。化合物CpY(μ-CH)(μ-CH)(μ-H)(thf)表现出“施罗克型”亲核卡宾反应性，将酮转化为相应的末端烯烃。用[D]甲醇处理Cp*Y(μ-CH)(μ-CH)(μ-H)(thf)证明了所有小分子官能团的可及性，氘代HD、氘代甲烷CHD和CHD的同时形成表明了这一点。
