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IR Spectra and DFT Calculations of M–η 2 ‐(NC)–CH 3 , CH 3 –MNC, and CH 2 =M(H)NC Prepared by Reactions of Laser‐Ablated Hf and Ti Atoms with Acetonitrile
Author(s) -
Cho HanGook,
Andrews Lester
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500624
Subject(s) - chemistry , agostic interaction , acetonitrile , acetylene , ethylene , halide , metal , nitrile , group 2 organometallic chemistry , crystallography , inorganic chemistry , molecule , organic chemistry , catalysis
Laser‐ablated Hf and Ti atoms produce M–η 2 ‐(NC)–CH 3 , CH 3 –MNC, and CH 2 =M(H)NC in reactions with acetonitrile, parallel to the earlier Zr results, based on isotopic substitution and frequencies computed by DFT. These products are the most stable components in the previously proposed reaction path for reactions of metal atoms with acetonitrile, in line with the observed products in other metal systems and DFT calculations. Other plausible products [CH 3 CN–M and CH≡M(H 2 )NC] are energetically too high to be generated in reactions of the group 4 metals. The group 4 metals form strong π complexes with the nitrile group as they do with acetylene and ethylene. The methylidenes are slightly more agostic due to the metal‐containing conjugation system than those produced from small alkanes and methyl halides. Relativistic contraction is also evident in that the Hf bonds are shorter than the Zr bonds.