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Infrared Spectra of the η2-M(NC)-CH3, CH3-MNC, and CH2M(H)NC Complexes Prepared by Reactions of Thorium and Uranium Atoms with Acetonitrile

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journal contribution
posted on 23.01.2012, 00:00 authored by Han-Gook Cho, Lester Andrews
The η2-M­(NC)-CH3, CH3-MNC, and CH2M­(H)­NC complexes are observed in the matrix IR spectra from reactions of laser-ablated Th and U atoms with acetonitrile. These actinide products are in line with those from reactions of group 4–6 metals with acetonitrile, and they are again the most stable steps in the previously proposed reaction path. The N-coordination and methylidyne products (M←NCCH3 and HCM­(H)2NC) are not observed probably due to their high energies. The actinide methylidenes show agostic distortion, and the nitrile π-complexes (η2-M­(NC)-CH3) support strong back-donations to the π*-orbitals. NBO analysis reveals single M–N and M–C bonds with full σ- and π-bonds in the NC subunit. The unidentified N-coordinated-acetonitrile complexes show strong calculated interactions with these early actinide atoms.