Department of Chemistry, University of Incheon, 12-1 Songdo-dong, Yonsu-ku, Incheon 406-840, South Korea.
J Phys Chem A. 2010 Sep 23;114(37):10028-39. doi: 10.1021/jp102666h.
The ethynyl metal hydride (HC≡C−MH) and metallacycle complexes (M-η2-(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-η2-(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.
在激光烧蚀的第 5 族金属原子与乙炔反应的基质红外光谱中，鉴定出了炔基金属氢化物（HC≡C-MH）和金属茂络合物（M-η2-（C2H2））。观察到的强度变化表明，环状络合物在退火时会自发形成，并通过氧化 C-H 插入反应以及随后的光解转化为插入产物。未鉴定出较不稳定的亚乙烯基络合物。第 5 族金属 M-η2-（C2H2）物种的高结合能、低 C-C 伸缩频率和长 C-C 键都表明与后过渡金属和轻金属类似物相比，它们具有较强的键合能力，但与第 4 族金属类似物相比，它们的键合能力略弱。
