4.8 Article

Activation of H2 over the Ru-Zn Bond in the Transition Metal-Lewis Acid Heterobimetallic Species [Ru(IPr)2(CO)ZnEt]+

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 35, 页码 11081-11084

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AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b05243

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资金

  1. EPSRC [EP/J009962/1]
  2. Heriot-Watt University
  3. Engineering and Physical Sciences Research Council [EP/J009962/1] Funding Source: researchfish
  4. EPSRC [EP/J009962/1] Funding Source: UKRI

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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.

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