Infrared Spectra of the CH3−MX and CH2−MHX Complexes Formed by Reactions of Laser-Ablated Group 3 Metal Atoms with Methyl Halides
journal contributionposted on 05.04.2007, 00:00 by Han-Gook Cho, Lester Andrews
Reactions of laser-ablated group 3 metal atoms with methyl halides have been carried out in excess of Ar during condensation and the matrix infrared spectra studied. The metals are as effective as other early transition metals in providing insertion products (CH3−MX) and higher oxidation state methylidene complexes (CH2−MHX) (X = F, Cl, Br) following α-hydrogen migration. Unlike the cases of the group 4−6 metals, the calculated methylidene complex structures show little evidence for agostic distortion, consistent with the previously studied group 3 metal methylidene hydrides, and the C−M bond lengths of the insertion and methylidene complexes are comparable to each other. However, the C−Sc bond lengths are 0.013, 0.025, and 0.029 Å shorter for the CH2−ScHX complexes, respectively, and the spin densities are consistent with weak C(2p)−Sc(3d) π bonding. The present results reconfirm that the number of valence electrons on the metal is important for agostic interaction in simple methylidene complexes.