%0 Journal Article
%A Cho, Han-Gook
%A Andrews, Lester
%D 2012
%T 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
%U https://acs.figshare.com/articles/journal_contribution/Infrared_Spectra_of_the_Complexes_Os_NCCH_sub_3_sub_Re_NCCH_sub_3_sub_CH_sub_3_sub_ReNC_CH_sub_2_sub_Re_H_NC_and_CH_Re_H_sub_2_sub_NC_and_their_Mn_Counterparts_Prepared_by_Reactions_of_Laser_Ablated_Os_Re_and_Mn_Atoms_with_Acetonitrile_in_Excess_Argon/2488723
%R 10.1021/om300456k.s001
%2 https://acs.figshare.com/ndownloader/files/4131511
%K Infrared Spectra
%K HC
%K halide analogues
%K UV irradiation
%K agostic interaction
%K H migration
%K counterpart product absorptions
%K CH
%K methylidyne product
%K methylidyne complexes
%K Mn Counterparts
%K Mn Atoms
%K Excess ArgonAcetonitrile forms
%K Re metal atoms
%K isocyanide system
%K metal atoms
%X Acetonitrile 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.
%I ACS Publications