Infrared spectra of small insertion and methylidene complexes in reactions of laser-ablated nickel atoms with halomethanes

Han Gook Cho, Lester Andrews, Bess Vlaisavljevich, Laura Gagliardi

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Abstract

Nickel carbene complexes, CX2=NiX2, are prepared along with the insertion products, CX3-NiX, in reactions of laser-ablated Ni atoms with tetrahalomethanes. These reaction products are identified from matrix infrared spectra and density functional frequency calculations. In agreement with the previously studied Pt cases, the carbon-nickel bonds of the Ni carbene complexes are essentially double bonds with CASPT2-computed effective bond orders of 1.8-1.9. On the other hand, only insertion complexes are generated from dihalomethane and trihalomethane precursors. The nickel carbenes have staggered structures, and several insertion complexes containing C-Cl bonds reveal distinct bridged structures similar to those observed in the corresponding Fe products, which indicate effective coordination of Cl to the metal center. The unique F-bridged CH 2F-NiCl structure is also observed.

Original languageEnglish (US)
Pages (from-to)5623-5632
Number of pages10
JournalOrganometallics
Volume28
Issue number19
DOIs
StatePublished - Oct 12 2009

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