Pontiggia, Ashley J., Chaplin, Adrian B. and Weller, Andrew S.. (2011) Cationic iridium complexes of the Xantphos ligand. Flexible coordination modes and the isolation of the hydride insertion product with an alkene. Journal of Organometallic Chemistry, Vol.696 (No.17). pp. 2870-2876. ISSN 0022-328X

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Abstract

Reaction of the Ir(I)-Xantphos complex [Ir(kappa(2)-Xantphos)(COD)][BAr(4)(F)] (Xantphos - 4,5-bis(diphenyl-phosphino)-9,9-dimethylxanthene, Ar(F) = C(6)H(3)(CF(3))(2)) with H(2) in acetone or CH(2)Cl(2)/ MeCN affords the Ir(III)-hydrido complexes [Ir(kappa(3)-Xantphos)(H)(2)(L)][BAr(4)(F)], L = acetone or MeCN, whereas in non-coordinating CH(2)Cl(2) solvent dimeric [Ir(kappa(3)-Xantphos)(H)(mu-H)](2)[BAr(4)(F)](2) is formed. A common intermediate in these reactions that invokes a (sigma, eta(2)-C(8)H(13)) ligand is reported. Addition of excess tert-butylethene (tbe) to [Ir(kappa(3)-Xantphos)(H)(2)(MeCN)][BAr(4)(F)] results in insertion of a hydride into the alkene to form [Ir(kappa(3)-Xantphos)(MeCN)(CH(2)CH(2)C(CH(3))(3))(H)][BAr(4)(F)], an Ir(III) alkyl-hydrido-Xantphos complex. This reaction is reversible, and heating (80 degrees C) results in the reformation of [Ir(kappa(3)-Xantphos)(H)(2)(MeCN)][BAr(4)(F)] and tbe. These complexes have been characterised by NMR spectroscopy, ESI-MS and single-crystal X-ray diffraction. They show variable coordination modes of the Xantphos ligand: cis-kappa(2)-P,P, fac-kappa(3)-P,O,P and mer-kappa(3)-P,O,P with the later coordination mode like that found in related PNP-pincer complexes. (C) 2011 Elsevier B.V. All rights reserved.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH):	Iridium, Phosphine, Ligands, Hydrides, Organophosphorus compounds
Journal or Publication Title:	Journal of Organometallic Chemistry
Publisher:	Elsevier Science SA
ISSN:	0022-328X
Date:	15 August 2011
Volume:	Vol.696
Number:	No.17
Page Range:	pp. 2870-2876
Identification Number:	10.1016/j.jorganchem.2011.01.036
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Funder:	University of Oxford, Engineering and Physical Sciences Research Council (EPSRC)
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URI:	http://wrap.warwick.ac.uk/id/eprint/40495

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