Pécharman Anne-Frédérique, Carpentier Ambre, Lowe John P, Macgregor Stuart A, Mahon Mary F, Whittlesey Michael K
Department of Chemistry, University of Bath, Bath BA2 7AY, United Kingdom.
Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, United Kingdom.
Inorg Chem. 2025 Mar 3;64(8):4043-4051. doi: 10.1021/acs.inorgchem.4c05360. Epub 2025 Feb 19.
Reaction of [Ru(IPr)(CO)H][BAr] (; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BAr = B{3,5(CF)CH}) with an excess of ZnH in THF gives the structurally characterized neutral Ru(ZnH) complex [Ru(IPr)(CO)(ZnH)H] () and Ru(ZnH) salt [Ru(IPr)(CO)(ZnH)H][BAr] (). Crystallographic and computational analyses show the presence of both bridging Ru-H-Zn hydrides and terminal Ru-hydrides in the two products. Calculations also identify a low-energy H/ZnH exchange pathway that rationalizes the experimentally observed (EXSY) fluxionality of the hydrides in . At room temperature, this compound undergoes stoichiometric exchange with ZnMe to give [Ru(IPr)(CO)(ZnMe)H][BAr] (), and also proves to be catalytically active for the hydrogenation of 1-hexene and 5-hexene-2-one.
[Ru(IPr)(CO)H][BAr]（；IPr = 1,3-双(2,6-二异丙基苯基)咪唑-2-亚基；BAr = B{3,5-(CF₃)₂C₆H₃}）与过量的ZnH₂在四氢呋喃中反应，得到结构表征的中性Ru(ZnH)配合物[Ru(IPr)(CO)(ZnH)H]（）和Ru(ZnH)盐[Ru(IPr)(CO)(ZnH)H][BAr]（）。晶体学和计算分析表明，两种产物中均存在桥连Ru-H-Zn氢化物和末端Ru-氢化物。计算还确定了一条低能量的H/ZnH交换途径，该途径合理化了实验观察到的（EXSY）中氢化物的流动性。在室温下，该化合物与ZnMe₂进行化学计量交换，生成[Ru(IPr)(CO)(ZnMe)H][BAr]（），并且还被证明对1-己烯和5-己烯-2-酮的氢化具有催化活性。
