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

Authors
Cho, Han-Gook
Andrews, Lester
Vlaisavljevich, Bess
Published in Organometallics. 2009, vol. 28, no. 24, p. 5623-5632
Abstract Nickel carbene complexes,CX2dNiX2, 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 CH2F-NiCl structure is also observed.
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CHO, Han-Gook et al. Infrared spectra of small insertion and methylidene complexes in reactions of laser-ablated palladium atoms with halomethanes. In: Organometallics, 2009, vol. 28, n° 24, p. 5623-5632. https://archive-ouverte.unige.ch/unige:6464

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Deposited on : 2010-05-04

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