Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh 3 ) 2 (ZnMe) 4 H 2 ]
Zinc-Promoted ZnMe/ZnPh Exchange in Eight-Coordinate [Ru(PPh 3 ) 2 (ZnMe) 4 H 2 ]
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锌促进的八配位 ZnMe/ZnPh 交换 [Ru(PPh 3 ) 2 (ZnMe) 4 H 2 ]
DOI：
10.1002/ange.202117495
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发表时间：
2022
影响因子：
--
通讯作者：
Sotorrios L
中科院分区：
文献类型：
--
作者：
Sotorrios L
报道了[Ru(PPh3)2(ZnMe)4H2]、[Ru(PPh3)2(ZnPh)4H2]、[Ru(PPh3)2(ZnPh)4H2]、[Ru(PPh3)2(ZnPh)4H2]、[Ru(PPh3)2(ZnPh)4H2]的合成、反应性和电子结构分析。1 - a具有8 -座标Ru中心，轴向磷化氢和ZnMe配体在赤道面上对称（2:1）排列。ZnMe配体in1与znph2进行了简单的顺序交换，得到了ZnPh配体的3∶1排列。1和2都与它们各自的3:1和2:1异构体平衡存在。利用DFT计算提出了ZnMe/ZnPh交换和异构化的机理。讨论了根岸反应中这些{Ru(ZnR)4H2}物质与等电子8族过渡金属多氢化物的关系及相关的Schlenk平衡。
The syntheses, reactivity and electronic structure analyses of [Ru(PPh3)2(ZnMe)4H2],1 a, and [Ru(PPh3)2(ZnPh)4H2],2 b, are reported.1 aexhibits an 8‐coordinate Ru centre with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe ligands in1 aundergo facile, sequential exchange with ZnPh2to give2 b, which shows a 3 : 1 arrangement of ZnPh ligands. Both1 aand2 bexist in equilibrium with their respective 3 : 1 and 2 : 2 isomers. Mechanisms for ZnMe/ZnPh exchange and isomerisation are proposed using DFT calculations. The relationships of these {Ru(ZnR)4H2} species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed.