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基于三苯基膦的[钌-铝]和[钌-锡]异双金属配合物的结构与反应活性

Structure and Reactivity of [Ru-Al] and [Ru-Sn] Heterobimetallic PPh-Based Complexes.

作者信息

Isaac Connie J, Miloserdov Fedor M, Pécharman Anne-Frédérique, Lowe John P, McMullin Claire L, Whittlesey Michael K

机构信息

Department of Chemistry, University of Bath, Bath BA2 7AY, U.K.

出版信息

Organometallics. 2022 Oct 10;41(19):2716-2730. doi: 10.1021/acs.organomet.2c00344. Epub 2022 Sep 21.

DOI:10.1021/acs.organomet.2c00344
PMID:36249448
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9554919/
Abstract

Treatment of [Ru(PPh)(CHPPh)H][Li(THF)] with AlMeCl and SnMeCl leads to elimination of LiCl and CH and formation of the heterobimetallic complexes [Ru(CHPPh){PPhCHAlMe(THF)}H] and [Ru(PPh)(CHPPh)(PPhCHSnMe)] , respectively. The pathways to and have been probed by variable temperature NMR studies, together with input from DFT calculations. Complete reaction of H occurs with at 60 °C and with at room temperature to yield the spectroscopically characterized trihydride complexes [Ru(PPh){PPhCHAlMe}H] and [Ru(PPh){PPhCHSnMe}H] . In the presence of CO, forms the acylated phosphine complex, [Ru(CO)(C(O)CHPPh)(PPhCHSnMe)] , through a series of intermediates that were identified by NMR spectroscopy in conjunction with CO labeling. Complex undergoes addition and substitution reactions with the N-heterocyclic carbene 1,3,4,5-tetramethylimidazol-2-ylidene (IMe) to give [Ru(IMe)(PPhCH)(PPhCHSnMe)] , which converted via rare N-Me group C-H activation to [Ru(IMe)(PPh)(IMe)'(PPhCHSnMe)] upon heating at 60 °C and to a mixture of [Ru(IMe)(IMe)'(PPhCHSnMe)] and [Ru(PPh)(PPhCH)(IMe-SnMe)'] at 120 °C.

摘要

用AlMeCl和SnMeCl处理[Ru(PPh)(CHPPh)H][Li(THF)]会导致LiCl和CH消除，并分别形成异双金属配合物[Ru(CHPPh){PPhCHAlMe(THF)}H]和[Ru(PPh)(CHPPh)(PPhCHSnMe)]。通过变温核磁共振研究以及密度泛函理论计算的输入，对形成这两种配合物的途径进行了探究。H与在60℃下完全反应，与在室温下完全反应，生成经光谱表征的三氢化物配合物[Ru(PPh){PPhCHAlMe}H]和[Ru(PPh){PPhCHSnMe}H]。在CO存在下，通过一系列经核磁共振光谱结合CO标记鉴定的中间体，形成酰化膦配合物[Ru(CO)(C(O)CHPPh)(PPhCHSnMe)]。配合物与N-杂环卡宾1,3,4,5-四甲基咪唑-2-亚基（IMe）发生加成和取代反应，生成[Ru(IMe)(PPhCH)(PPhCHSnMe)]，在60℃加热时通过罕见的N-Me基团C-H活化转化为[Ru(IMe)(PPh)(IMe)'(PPhCHSnMe)]，在120℃时转化为[Ru(IMe)(IMe)'(PPhCHSnMe)]和[Ru(PPh)(PPhCH)(IMe-SnMe)']的混合物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1539/9554919/69e679937af0/om2c00344_0015.jpg
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