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Issue 35, 2011
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Rhodium and iridium complexes of an asymmetric bicyclic NHC bearing secondary pyridyl donors

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Abstract

A tridentate N⁁C⁁N ligand, 1, containing a bicyclic central NHC ring and two flanking pyridyl groups has been coordinated to Rh(I) and Ir(I) to give complexes of the type [M(κ3-1)(1,5-COD)]PF6 (2 M = Rh; 3 M = Ir). In contrast to our earlier study with this ligand, the complexes have been shown to approximate to a trigonal bipyramidal geometry in the solid state and exist as an isomeric mixture in solution as determined by 1H and 13C NMR spectroscopy. Electrochemical studies revealed that both complexes undergo a 1-electron oxidation with the potential of the Rh complex 0.1V less than that of the Ir complex in CH2Cl2. Preliminary DFT studies confirm the lowest energy conformations as those seen in the solid state and show the location and energy of the HOMOs to be identical in 2 and 3. Partial charge analysis shows a greater positive charge on the Ir in 3 compared to the Rh in 2. Some preliminary studies of hydrogenation reactivity have shown the complexes to be efficient for both transfer and direct hydrogenation of prochiral ketones and alkenes at moderate temperatures but without any discernible enantioselectivity.

Graphical abstract: Rhodium and iridium complexes of an asymmetric bicyclic NHC bearing secondary pyridyl donors

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Supplementary files

Article information


Submitted
05 Apr 2011
Accepted
10 May 2011
First published
20 Jun 2011

Dalton Trans., 2011,40, 8807-8813
Article type
Paper

Rhodium and iridium complexes of an asymmetric bicyclic NHC bearing secondary pyridyl donors

P. D. Newman, K. J. Cavell, A. J. Hallett and B. M. Kariuki, Dalton Trans., 2011, 40, 8807
DOI: 10.1039/C1DT10582E

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