The Library
Cationic iridium complexes of the Xantphos ligand. Flexible coordination modes and the isolation of the hydride insertion product with an alkene
Tools
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. doi:10.1016/j.jorganchem.2011.01.036 ISSN 0022-328X.
Research output not available from this repository.
Request-a-Copy directly from author or use local Library Get it For Me service.
Official URL: http://dx.doi.org/10.1016/j.jorganchem.2011.01.036
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, Engineering and Medicine > 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 | ||||
Official Date: | 15 August 2011 | ||||
Dates: |
|
||||
Volume: | Vol.696 | ||||
Number: | No.17 | ||||
Page Range: | pp. 2870-2876 | ||||
DOI: | 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) |
Data sourced from Thomson Reuters' Web of Knowledge
Request changes or add full text files to a record
Repository staff actions (login required)
View Item |