m3-h2:h2:h2-Coordination of Primary Silane on a Triruthenium Plane
m3-h2:h2:h2-Coordination of Primary Silane on a Triruthenium Plane
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m3-h2:h2:h2-伯硅烷在三钌平面上的配位
DOI：
10.1002/anie.201506969
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发表时间：
2015
期刊：
影响因子：
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通讯作者：
Toshiro Takao
中科院分区：
文献类型：
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作者：
Masahiro Nagaoka;Hiroyuki Tsuruda;Masa-aki Amako;Hiroharu Suzuki;Toshiro Takao
一个3μη2:η2:η2高硅烷复杂[(Cp *俄文)3(3μη2:应承担的η2:η2必经H3SitBu)(μ检测H) 3] (2; Cp * =η5必经C5Me5),合成反应的[{Cp *俄文(μ检测H)} 3(μ3 H)应承担2](1)withtBuSiH3。配合物2是硅烷配体采用μ3‐η2:η2:η2配位模式的第一个例子。这种史无前例的配位模式是通过核磁共振和红外光谱以及X射线衍射分析建立的，并得到了密度函数研究的支持。变温核磁共振分析表明，2与互变异构μ3 -硅基络合物（3a）平衡。虽然没有分离到3a，但与PhSiH3反应得到了相应的μ3‐硅基配合物[(Cp*Ru)3(μ3‐η2:η2‐H2SiPh)(H)(μ‐H)3] （3b）。用phsih3处理2a导致硅烷交换反应，形成3杆菌并消除busih3。这一结果表明，μ3‐硅烷配合物可以看作是氧化加成/还原消除伯硅烷到三核位点的“截留”中间体。
A μ3‐η2:η2:η2‐silane complex, [(Cp*Ru)3(μ3‐η2:η2:η2‐H3SitBu)(μ‐H)3] (2 a; Cp*=η5‐C5Me5), was synthesized from the reaction of [{Cp*Ru(μ‐H)}3(μ3‐H)2] (1) withtBuSiH3. Complex2 ais the first example of a silane ligand adopting a μ3‐η2:η2:η2coordination mode. This unprecedented coordination mode was established by NMR and IR spectroscopy as well as X‐ray diffraction analysis and supported by a density functional study. Variable‐temperature NMR analysis implied that2 aequilibrates with a tautomeric μ3‐silyl complex (3 a). Although3 awas not isolated, the corresponding μ3‐silyl complex, [(Cp*Ru)3(μ3‐η2:η2‐H2SiPh)(H)(μ‐H)3] (3 b), was obtained from the reaction of1with PhSiH3. Treatment of2 awith PhSiH3resulted in a silane exchange reaction, leading to the formation of3 baccompanied by the elimination oftBuSiH3. This result indicates that the μ3‐silane complex can be regarded as an “arrested” intermediate for the oxidative addition/reductive elimination of a primary silane to a trinuclear site.