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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Reactions of [Cu(X)(BPEP-Ph)] (X = PF6, SbF6) with silyl compounds. Cooperative bond activation involving non-coordinating anions
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Reactions of [Cu(X)(BPEP-Ph)] (X = PF6, SbF6) with silyl compounds. Cooperative bond activation involving non-coordinating anions

机译：[Cu（X）（BPEP-Ph）]（X = PF6，SbF6）与甲硅烷基化合物的反应。涉及非配位阴离子的协同键活化

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摘要

Bond activation of silyl compounds, assisted by the cooperative action of non-coordinating anions, is achieved using Cu(I) complexes coordinated with a PNP-pincer type phosphaalkene ligand, [Cu(X)( BPEP-Ph)] (X = PF6 (1a), SbF6 (1b); BPEP-Ph = 2,6-bis[1-phenyl-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyl] pyridine). Complexes 1a and 1b react with Me3SiCN to form Me3SiF and Cu(I) cyanide complexes of the formula [Cu(CN-EF5)(BPEP-Ph)] (E = P (2a), Sb (2b)), in which the CN ligand is associated with the EF5 group arising from EF6-. Formation of the intermediary isonitrile complex [Cu(CNSiMe3)(BPEP-Ph)]+ SbF6 (3b) is confirmed by its isolation. Thus, a two-step reaction process involving coordination of Me3SiCN, followed by nucleophilic attack of SbF6- on the silicon atom of 3b is established for the conversion of 1b to 2b. Complex 1b cleaves the H-Si bond of PhMe2SiH as well. The isolation and structural identification of [Cu(BPEP-Ph)]+ BAr4F- (1c) (BAr4F = B{3,5-(CF3)(2)C6H3}(4)) as a rare example of a T-shaped, three-coordinated Cu(I) complex is reported.
机译：甲硅烷基化合物的键活化，借助非配位阴离子的协同作用，可通过与PNP-钳子型磷烯烃配体[Cu（X）（BPEP-Ph）]配位的Cu（I）配合物实现（X = PF6 （1a），SbF 6（1b）; BPEP-Ph ＝ 2，6-双[1-苯基-2-（2，4，6-三叔丁基苯基）-2-磷乙烯基]吡啶）。配合物1a和1b与Me3SiCN反应形成式[Cu（CN-EF5）（BPEP-Ph）]（E = P（2a），Sb（2b））的Me3SiF和Cu（I）氰化物配合物。 CN配体与源自EF6-的EF5基团相关。中间异腈复合物[Cu（CNSiMe3）（BPEP-Ph）] + SbF6（3b）的形成通过其分离得到证实。因此，建立了一个两步反应过程，涉及Me3SiCN的配位，然后发生SbF6-对3b的硅原子的亲核攻击，从而将1b转化为2b。配合物1b也会裂解PhMe2SiH的H-Si键。 T形的罕见实例[Cu（BPEP-Ph）] + BAr4F-（1c）（BAr4F = B {3,5-（CF3）（2）C6H3}（4））的分离和结构鉴定，报道了三配位的Cu（I）配合物。

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