包含甲基、亚甲基和氢配体的稀土金属半夹心配合物。
Rare-earth-metal half-sandwich complexes incorporating methyl, methylidene, and hydrido ligands.
作者信息
Buschmann Dennis A, Schumacher Lion, Anwander Reiner
机构信息
Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany.
出版信息
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。
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