Activation of H-2 over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)(2)(CO)ZnEt](+)

作者：Riddlestone Ian M; Rajabi Nasir A; Lowe John P; Mahon Mary F; Macgregor Stuart A^*; Whittlesey Michael K^*

来源：Journal of the American Chemical Society, 2016, 138(35): 11081-11084.

DOI：10.1021/jacs.6b05243

Reaction of [Ru(IPr)(2)(CO)H]BAr4F with ZnEt2 forms the heterobimetallic species [Ru(IPr)(2)(CO)-ZnEt]BAr4F (2), which features an unsupported Ru-Zn bond. 2 reacts with H-2 to give [Ru(IPr)(2)(CO)(eta(2)-H-2)-(H)(2)ZnEt]BAr4F (3) and [Ru(IPr)(2)(CO)(H)(2)ZnEt]BArP4 (4). DFT calculations indicate that H-2 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.

• 出版日期2016-9-7