Metal-Silicon Triple Bonds: Access to [Si(η5-C5Me5)]+ from SiX2(NHC) and its Conversion to the Silylidyne Complex (TpMe(CO)2MoSi(η3-C5Me5)] (TpMe = κ3-N,N',N" -hydridotris(3,5-dimethyl-1-pyrazolyl)borate)
Metal-Silicon Triple Bonds: Access to [Si(η5-C5Me5)]+ from SiX2(NHC) and its Conversion to the Silylidyne Complex (TpMe(CO)2MoSi(η3-C5Me5)] (TpMe = κ3-N,N',N" -hydridotris(3,5-dimethyl-1-pyrazolyl)borate)
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DOI：
10.1021/acs.organomet.7b00665
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发表时间：
2018-03-12
期刊：
影响因子：
2.8
通讯作者：
Filippou, Alexander C.
中科院分区：
文献类型：
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作者：
Ghana, Priyabrata;Arz, Marius I.;Filippou, Alexander C.
提出了一种合成SiCp*(2)(1)(Cp*=C5Me5)的新方法，该方法涉及N-杂环卡宾(NHC)稳定的Si-II卤化物SiX2(NHC)(X=Cl，Br)与2当量KCP*的反应。该路线是目前已知的费力、多步合成1的一种更好的替代方法，并通过1与[H(Et2O)(2)]-[B(C6F5)(4)]的选择性质子化提供了多克规模的容易获得[Si(ETA(5)-Cp*)][B(C6F5)(4)](2)的途径。2与金属配合物Na[Tp(Me)Mo(CO)(2)(PMe3)]反应，得到了前所未有的硅烷络合物[Tp(Me)(CO)(2)MoSi(ETA(3)-Cp*)](3；Tp(Me)=kappa(3)-N，N‘，N“-氢化物(3，5-二甲基-1-吡唑基)-硼酸盐)。单晶X射线衍射和光谱研究，结合量子化学计算，揭示了化合物3独特的成键情况，其特征是具有部分三键性质的离域Mo-Si键和与硅配位的Cp*取代基。
A novel method to prepare SiCp*(2) (1) (Cp* = C5Me5) is presented involving the reaction of N-heterocyclic carbene (NHC)-stabilized Si-II halides SiX2(NHC) (X = Cl, Br) with 2 equiv of KCp*. This route is a superior alternative to the laborious, multistep synthesis of 1 presently known and provides via the selective protonolysis of 1 with [H(Et2O)(2)]-[B(C6F5)(4)] facile access to [Si(eta(5)-Cp*)][B(C6F5)(4)] (2) in multigram scale and high yield. Reaction of 2 with the tailored metallate Na[Tp(Me)Mo(CO)(2)(PMe3)] afforded the unprecedented silylidyne complex [Tp(Me)(CO)(2)MoSi(eta(3)-Cp*)] (3; Tp(Me) = kappa(3)-N,N',N"-hydridotris (3,5-dimethyl-1-pyrazolyl)-borate). Single crystal X-ray diffraction and spectroscopic studies in combination with quantum chemical calculations shed light on the unique bonding situation of 3 featuring a delocalized Mo-Si bond with partial triple bond character and a Cp* substituent, which is eta(3)-coordinated to silicon.