Low-Coordinate Cobalt Fluoride Complexes: Synthesis, Reactions, and Production from C–F Activation Reactions
作者:Thomas R. Dugan、Jonathan M. Goldberg、William W. Brennessel、Patrick L. Holland
DOI:10.1021/om200991k
日期:2012.2.27
mechanism beginning with rate-limiting oxidative addition of the aryl fluoride to cobalt(I), followed by rapid reduction of the cobalt(III) aryl fluoride intermediate by a second molecule of LtBuCo. [LtBuCo(μ-F)]2 also reacts with Et3SiH to give the hydride complex [LtBuCo(μ-H)]2. This hydride complex has low reactivity toward alkenes and N2, in contrast to an earlier report.
氟化钴(II)络合物,[L t Bu Co(μ-F)] 2 [L t Bu = 2,2,6,6-四甲基-3,5-双(2,6-二异丙基苯基亚氨基)庚烷4基],被从L-合成吨卜联合使用我3经由的SnF键的均裂的SnF。L t Bu Co还执行了氟化芳烃的整体双核氧化加成反应,得到摩尔比为1:2的[L t Bu Co(μ-F)] 2和相应氟苯底物的钴(II)芳基络合物。C–F活化反应对钴和氟苯的浓度都具有一级速率依赖性。该速率由meta增加-氟化物取代基,以及被邻-氟化物取代物减慢的速度,分别表明电子和位阻对过渡态的影响。这些数据与一个机构开头限速氧化加成的芳基氟化物,以钴最一致的(I),随后快速还原钴(III)的氟化芳基中间体由L的第二分子吨卜公司[L t Bu Co(μ-F)] 2也与Et 3 SiH反应生成氢化物配合物[L t Bu Co(μ-H)] 2。与较早的报道相反,该氢化物配合物对烯烃和N
Reaction of hexamethylditin with dimethyltin dichloride
作者:Matthew J. Cuthbertson、Peter R. Wells
DOI:10.1016/s0022-328x(00)85815-5
日期:1981.8
Hexamethylditin in methanol solution reacts with dimethyltindichloride to yield as major products trimethyltin chloride and polymeric materials whose composition depends upon the molar ratio of the reactants. Tetramethylditin dichloride is a significant minor product together with small amounts of various intermediates which have been tentatively identified. The stoichiometry of the reaction has been