Issue 23, 2010

Infrared spectra of XC[triple bond, length as m-dash]IrX3 and CX2[double bond, length as m-dash]IrX2 prepared by reactions of laser-ablated iridium atoms with halomethanes

Abstract

Small iridium high oxidation-state complexes with carboniridium multiple bonds are identified in the product matrix infrared spectra from reactions of laser-ablated Ir atoms with tetra-, tri- and dihalomethanes. In contrast to the previously studied Rh case, Ir carbyne complexes (XC[triple bond, length as m-dash]IrX3) are generated in reactions of tetrahalomethanes, and their short Ir–C bond lengths of 1.725–1.736 Å are appropriate for the carbon–metal triple bonds. DFT calculations also show that the Ir carbynes with an Ir–F bond have unusual square planar structures, similar to the recently discovered Ru planar complexes. Diminishing preference for the carbyne complexes leads to methylidene product absorptions in the tri- and dihalomethane spectra, marking a limit for generation of small metal carbynes. The insertion complexes, on the other hand, are not observed in this study, suggesting that X migration from C to Ir following initial C–X insertion is swift.

Graphical abstract: Infrared spectra of XC [[triple bond, length as m-dash]] IrX3 and CX2 [[double bond, length as m-dash]] IrX2 prepared by reactions of laser-ablated iridium atoms with halomethanes

Supplementary files

Article information

Article type
Paper
Submitted
04 Feb 2010
Accepted
13 Apr 2010
First published
05 May 2010

Dalton Trans., 2010,39, 5478-5489

Infrared spectra of XC[triple bond, length as m-dash]IrX3 and CX2[double bond, length as m-dash]IrX2 prepared by reactions of laser-ablated iridium atoms with halomethanes

H. Cho and L. Andrews, Dalton Trans., 2010, 39, 5478 DOI: 10.1039/C002347G

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