Department of Chemistry, University of Bath , Claverton Down, Bath BA2 7AY, U.K.
Institute of Chemical Sciences, Heriot-Watt University , Edinburgh EH14 4AS, U.K.
J Am Chem Soc. 2016 Sep 7;138(35):11081-4. doi: 10.1021/jacs.6b05243. Epub 2016 Aug 26.
Reaction of [Ru(IPr)2(CO)H]BAr(F)4 with ZnEt2 forms the heterobimetallic species [Ru(IPr)2(CO)ZnEt]BAr(F)4 (2), which features an unsupported Ru-Zn bond. 2 reacts with H2 to give [Ru(IPr)2(CO)(η(2)-H2)(H)2ZnEt]BAr(F)4 (3) and [Ru(IPr)2(CO)(H)2ZnEt]BAr(F)4 (4). DFT calculations indicate that H2 activation at 2 proceeds via oxidative cleavage at Ru with concomitant hydride transfer to Zn. 2 can also activate hydridic E-H bonds (E = B, Si), and computed mechanisms for the facile H/H exchange processes observed in 3 and 4 are presented.
[Ru(IPr)2(CO)H]BAr(F)4 与 ZnEt2 反应生成了具有非支撑 Ru-Zn 键的杂双核物种[Ru(IPr)2(CO)ZnEt]BAr(F)4（2）。2 与 H2 反应生成了[Ru(IPr)2(CO)(η(2)-H2)(H)2ZnEt]BAr(F)4（3）和[Ru(IPr)2(CO)(H)2ZnEt]BAr(F)4（4）。DFT 计算表明，2 中 H2 的活化是通过 Ru 的氧化断裂进行的，同时氢转移到 Zn。2 还可以活化氢化物 E-H 键（E=B，Si），并提出了在 3 和 4 中观察到的易于发生的 H/H 交换过程的计算机制。
