Infrared Spectra of CHCN→M, M-η-(NC)-CH, CH-MNC Prepared by Reactions of Laser-Ablated Fe, Ru, and Pt Atoms with Acetonitrile in Excess Argon.

Reactions of laser-ablated Fe, Ru, and Pt atoms with acetonitrile have been carried out in excess argon, and the products identified in the matrix spectra. CHCN→Fe and Fe-η-(NC)-CH observed in the original deposition spectra converted to CH-FeNC on uv irradiation. CHCN→Ru, the only product detected in the Ru system, dissociated on uv irradiation, but was partly reproduced on subsequent visible irradiation and annealing. Similar behavior was found for CHCN→Pt. The major products (CH-FeNC, CHCN→Ru, and CHCN→Pt) are the most stable constituents in the previously proposed reaction path for Group 4, 5, 6, and 7 metal atoms and acetonitrile, parallel with the previous results. The Group 8 metal π-coordination products are weakly bound complexes due to limited back-donation to the π*-orbitals of CHCN. Calculations show that the Fe insertion product has a much less bent structure than the Ru analogue, in line with its higher s-character from the first row transition-metal to the C-Fe bond, and the group 8 metal methylidenes are not agostically distorted. The Pt to N bond in CHCN→Pt is the strongest of all the metals we have investigated owing in large part to its higher electron affinity, which prevents nitrogen lone pair density from entering the pi* orbitals of the C-N group.