A unique coordination of SiH4:: Isolation, characterization, and theoretical study of (PR3)2H2Ru(SiH4)RuH2(PR3)2
A unique coordination of SiH4:: Isolation, characterization, and theoretical study of (PR3)2H2Ru(SiH4)RuH2(PR3)2
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DOI：
10.1021/ja000223p
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发表时间：
2000-06-14
影响因子：
15
通讯作者：
Barthelat, JC
中科院分区：
文献类型：
--
作者：
Atheaux, I;Donnadieu, B;Barthelat, JC
自从1969年第一个硅烷σ-络合物的报道以来，Si-H键的活化一直是人们研究的热点。2，3硅烷的氢化硅烷化、氢化硅烷化和氢化聚合代表了最重要的应用并且涉及各种各样的硅烷。[4]然而，关于使用SiH 4（最简单的硅烷）和过渡金属的反应的出版物很少，这可能是安全问题的结果。唯一的过渡金属η2-SiH 4配合物Mo（η2-SiH 4）（CO）（R2 PC 2 H4 PR 2）2由Luo，Kubas等人于1995年报道。5该化合物通过SiH 4与钼配合物Mo（CO）（R2 PC 2 H4 PR 2）2直接反应获得。为了避免与使用SiH 4相关的任何危险，Harrod等人利用了通过Cp 2 TiMe 2催化再分布HSi（OEt）3而原位产生SiH 4。6这种烷氧基氢硅烷再分布也由锆和铪络合物催化，如蒂利等人所示。7在过去三年中，我们在分离特别是涉及一个以上σ键的不寻常配合物方面取得了很大进展。本文描述了一系列具有两个σ-Si-H键的双硅烷单核配合物[RuH_2 {（η_2-H-SiR_2）_2 X}（PR′_3）_2]，并证明了这些化合物是通过二级H → Si相互作用稳定的。8这些额外的相互作用也是另一种包含两个不同σ键RuH 2（η2-H2）（η 2-H2）的络合物的稳定性的原因。
Since the report of the first silane σ-complex in 1969, 1 the activation of Si-H bonds has been the focus of intense research effort. 2, 3 Hydrosilylation, dehydrogenative silylation, and dehydrogenative polymerization of silanes represent the most important applications and involve a wide variety of silanes. 4 However, the scarcity of publications on reactions using SiH4, the simplest silane, and transition metals is probably the result of safety concerns. The only transition metal η2-SiH4 complex Mo (η2-SiH4)(CO)(R2PC2H4PR2) 2 was reported in 1995 by Luo, Kubas et al. 5 This compound was obtained by direct reaction of SiH4 on the molybdenum complex Mo (CO)(R2PC2H4PR2) 2. To circumvent any hazard associated with the use of SiH4, its in situ generation by catalytic redistribution of HSi (OEt) 3 by Cp2TiMe2 was exploited by Harrod et al. 6 Such alkoxyhydrosilane redistributions were also catalyzed by zirconium and hafnium complexes as shown by Tilley et al. 7Within the last three years, we have made a lot of progress on the isolation of unusual complexes involving in particular more than one σ-bond. We have described a series of bis (silane) mononuclear complexes [RuH2 {(η2-H-SiR2) 2X}(PR′ 3) 2] with two σ-Si-H bonds and demonstrated that these compounds are stabilized by secondary H ‚‚‚Si interactions. 8 These additional interactions are also responsible for the stability of another complex incorporating two different σ-bonds RuH2 (η2-H2)(η2-