Highly Selective Substitution and Insertion Reactions of Silylenes in a Metal Coordinated Polyphosphide.

Highly Selective Substitution and Insertion Reactions of Silylenes in a Metal Coordinated Polyphosphide.
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金属配位多磷化物中硅烯的高选择性取代和插入反应

DOI:
10.1021/jacs.9b12151
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发表时间:
2020
影响因子:
15
通讯作者:
M. Scheer P. W. Roesky
M. Scheer P. W. Roesky
中科院分区:
化学1区
文献类型:
--
作者:
R. Yadav;T. Simler;S. Reichl;B. Goswami;C. Schoo;R. Köppe;M. Scheer P. W. Roesky

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本文报道了[Cp*Fe(η5-P5)]的环P5环上硅烯的选择性取代和插入反应。等电子[LSi]片段(L= PhC(NtBu)2)选择性取代一个P原子,得到[(η4-P4 SiL)FeCp*]和[LSi(Cl)nP-SiL(Cl)2]。为了阐明反应机理,合成了[{LSi(N(SiMe 3)2)}{(η4-P5)FeCp*}]作为反应中间体的模型化合物。将[LSi-SiL]插入[Cp*Fe(η5-P5)]的环P5环中,得到了[{η4-P5(SiL)2}FeCp*]的无环P5(SiL)2环,这是目前已知的最大的硅-多磷环。
Selective substitution and insertion reactions of silylenes into thecyclo-P5ring of [Cp*Fe(η5-P5)] are reported. The selective substitution of one P atom by an isoelectronic [LSi] fragment (L= PhC(NtBu)2) leads to [(η4-P4SiL)FeCp*] and [LSi(Cl)═P-SiL(Cl)2]. To elucidate the reaction mechanism, [{LSi(N(SiMe3)2)}{(η4-P5)FeCp*}], in which the silicon atom binds to thecyclo-P5ring, was synthesized as a model compound for the reaction intermediate. The insertion of [LSi-SiL] into thecyclo-P5ring of [Cp*Fe(η5-P5)] resulted in [{η4-P5(SiL)2}FeCp*] featuring acyclo-P5(SiL)2ring, which corresponds to the largest silicon–polyphosphorus ring known in a complex.
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发表时间: 2010-02
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影响因子: --
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