☆ 4.6 Article

Infrared Spectra of HC≡C-MH and M-η2-(C2H2) Produced in Reactions of Laser-Ablated Group 5 Transition-Metal Atoms with Acetylene

JOURNAL OF PHYSICAL CHEMISTRY A (2010)

期刊

JOURNAL OF PHYSICAL CHEMISTRY A

卷 114, 期 37, 页码 10028-10039

出版社

AMER CHEMICAL SOC

DOI: 10.1021/jp102666h

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Chemistry, Physical Physics, Atomic, Molecular & Chemical

资金

National Science Foundation (U.S.) [CHE 03-52487]
Korean government (MEST) [2010-0016527]
National Research Foundation of Korea [2009-0075428] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)

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摘要

The ethynyl metal hydride (HC equivalent to C-MH) and metallacycle complexes (M-eta(2)-(C2H2)) are identified in the matrix infrared spectra from reactions of laser-ablated group 5 metal atoms with acetylene. The observed intensity variations reveal spontaneous formation of the cyclic complex upon annealing and its conversion to the insertion product via oxidative C-H insertion reaction and also during subsequent photolysis. The less stable vinylidene complex is not identified. The high binding energies, low C-C stretching frequencies, and long C-C bonds of the group 5 metal M-eta(2)-(C2H2) species all indicate strong bonding relative to the late-transition-metal and light-metal analogues, but they are somewhat weaker than the group 4 metal counterparts.

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