om300456k_si_001.pdf (137.61 kB)
Infrared Spectra of the Complexes Os←NCCH3, Re←NCCH3, CH3–ReNC, CH2Re(H)NC, and CHRe(H)2NC and their Mn Counterparts Prepared by Reactions of Laser-Ablated Os, Re, and Mn Atoms with Acetonitrile in Excess Argon
journal contribution
posted on 2012-09-10, 00:00 authored by Han-Gook Cho, Lester AndrewsAcetonitrile forms primarily N-coordination complexes
(M←NCCH3) with Os and Re metal atoms, but these
metal atoms produce exclusively methylidyne complexes (HCMH2X) in similar previous reactions with small alkanes and halomethanes.
The Os complex increases on visible photolysis and dissociates partially
on UV irradiation without the generation of other new products, whereas
the Re complex converts to other products (CH3–ReNC,
CH2Re(H)NC, and CHRe(H)2NC)
on photolysis. The primary formation of the N-coordination complex
originates from its stability relative to that of the nitrile π-complex
in these systems. The agostic interaction in the methylidene complex
is apparently insignificant, and this rare observation of a methylidyne
product with Re reflects that H migration in the isocyanide system
is less favorable than those in the hydride and halide analogues.
Experiments with Mn gave weaker counterpart product absorptions.