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Issue 12, 2009
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Tungsten(0) and rhodium(I) complexes of a series of 2-(2′-halo)triarylphosphinines

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Abstract

A series of halo substituted triarylphosphinines have been synthesised and coordinated to tungsten(0) and rhodium(I) to give [(2-(2′-halo)-triarylphosphinine)W(CO)5] and [(2-(2′-halo)-triarylphosphinine)Rh(COD)Cl] respectively. The complexes have been examined by NMR and IR spectroscopy in an effort to elucidate the nature of the bonding between the phosphinines and the respective metal centre. The W(CO)5(L) systems reveal restricted C–C bond rotation as evidenced by temperature-dependent 31P{1H} NMR spectra. Thermodynamic barriers to the rotation are dependent upon the nature of the halide with ΔG values of 72.5 kJ mol−1 and 50.8 kJ mol−1 being obtained for the chloro- and fluoro-derivatives, respectively; activation barriers for the iodo- and bromo- derivatives were beyond the accessible temperature range of the NMR experiment.

Graphical abstract: Tungsten(0) and rhodium(I) complexes of a series of 2-(2′-halo)triarylphosphinines

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Article information


Submitted
22 Sep 2008
Accepted
25 Nov 2008
First published
06 Feb 2009

Dalton Trans., 2009, 2178-2184
Article type
Paper

Tungsten(0) and rhodium(I) complexes of a series of 2-(2′-halo)triarylphosphinines

C. Wallis, D. McGuinness, P. D. Newman, R. P. Tooze and P. G. Edwards, Dalton Trans., 2009, 2178
DOI: 10.1039/B816507F

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