Pt 上的 Si-H 和 Si-Si 活化：中性和阳离子硅基配合物的合成与反应性。

Si-H and Si-Si activation at Pt: synthesis and reactivity of neutral and cationic silyl complexes.

机构信息

Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Str. 2, 12489 Berlin, Germany.

出版信息

Dalton Trans. 2011 Dec 21;40(47):12699-704. doi: 10.1039/c1dt11351h. Epub 2011 Oct 11.

PMID:21989593

Abstract

Reactions of [Pt(PEt(3))(3)] (1) with the silanes HSiPh(3), HSiPh(2)Me and HSi(OEt)(3) led to the products of oxidative addition, cis-[Pt(H)(SiPh(3))(PEt(3))(2)] (2), cis-[Pt(H)(SiPh(2)Me)(PEt(3))(2)] (3), cis-[Pt(H){Si(OEt)(3)}(PEt(3))(2)] (cis-4) and trans-[Pt(H){Si(OEt)(3)}(PEt(3))(2)] (trans-4). The complexes cis-4 and trans-4 can also be generated by hydrogenolysis of (EtO)(3)SiSi(OEt)(3) in the presence of 1. Furthermore, the silyl compounds cis-4 and trans-4 react with B(C(6)F(5))(3) and CH(3)CN by hydride abstraction to give the cationic silyl complex trans-[Pt{Si(OEt)(3)}(NCCH(3))(PEt(3))(2)][HB(C(6)F(5))(3)] (8). In addition, the reactivity of the complexes cis-4, trans-4 and 8 towards alkenes and CO was studied using NMR experiments.

摘要

[Pt(PEt3)3]（1）与硅烷 HSiPh3、HSiPh2Me 和 HSi(OEt)3 的反应导致了氧化加成产物 cis-[Pt(H)(SiPh3)(PEt3)2]（2）、cis-[Pt(H)(SiPh2Me)(PEt3)2]（3）、cis-[Pt(H){Si(OEt)3}(PEt3)2]（cis-4）和 trans-[Pt(H){Si(OEt)3}(PEt3)2]（trans-4）的生成。在 1 的存在下，通过氢化（EtO）3SiSi（OEt）3 也可以生成配合物 cis-4 和 trans-4。此外，硅烷化合物 cis-4 和 trans-4 通过氢化物抽提与 B(C6F5)3 和 CH3CN 反应，生成阳离子硅烷配合物 trans-[Pt{Si(OEt)3}(NCCH3)(PEt3)2][HB(C6F5)3]（8）。此外，还通过 NMR 实验研究了配合物 cis-4、trans-4 和 8 对烯烃和 CO 的反应性。