Computational and Experimental Investigation of Alkene Hydrogenation by a Pincer-Type [P 2 Si]Rh Complex: Alkane Release via Competitive σ-Bond Metathesis and Reductive Elimination
Computational and Experimental Investigation of Alkene Hydrogenation by a Pincer-Type [P 2 Si]Rh Complex: Alkane Release via Competitive σ-Bond Metathesis and Reductive Elimination
复制标题
钳型 [P 2 Si]Rh 配合物对烯烃加氢的计算和实验研究：通过竞争性 Ï 键复分解和还原消除释放烷烃
DOI：
10.1021/acs.organomet.8b00922
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发表时间：
2019
期刊：
影响因子：
2.8
通讯作者：
Taylor, Buck L.
中科院分区：
文献类型：
--
作者：
Whited, Matthew T.;Trenerry, Michael J.;DeMeulenaere, Kaitlyn E.;Taylor, Buck L.
采用实验和计算相结合的方法研究了钳形[P2 Si]Rh催化剂的烯烃加氢反应机理。虽然[P2 Si]Rh与H2相互作用产生二氢σ-络合物而不是二氢化物（似乎是Rh（III）容易还原消除的迹象），但烷烃释放通过竞争性σ-键复分解（双分子）和还原消除（单分子）途径发生。这种不寻常的行为归因于甲硅烷基给体的强反式影响。
A combined experimental and computational approach has been utilized to elucidate the mechanism of alkene hydrogenation by pincer-type [P2Si]Rh catalysts. Although [P2Si]Rh interacts with H2to afford a dihydrogen σ-complex rather than a dihydride (seemingly an indication of facile reductive elimination from Rh(III)), alkane release occurs by competitive σ-bond metathesis (bimolecular) and reductive elimination (unimolecular) pathways. This unusual behavior is attributed to the strongtransinfluence of the silyl donor.