Moret, Séverine, Dallanegra, Romaeo, Chaplin, Adrian B., Douglas, Thomas M., Hiney, Rachel M. and Weller, Andrew S.. (2010) Alkyl dehydrogenation in iridium tri-cyclopentyl phosphines. Inorganica Chimica Acta, Vol.363 (No.3). pp. 574-580. ISSN 0020-1693

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Abstract

The iridium cyclooctadiene complex incorporating a tricyclopentyl phosphine ligand (PCyp(3)), Ir(eta(2):eta(2)-C(8)H(12))(PCyp(3))Cl, has been prepared. Removal of the chloride from this complex using Na[BAr(4)(F)][Ar(F) = C(6)H(3)(CF(3))(2)] in CH(2)Cl(2)/arene solvent results in dehydrogenation (C-H activation followed by beta-H transfer) of one of the alkyl phosphine rings and formation of the complexes [Ir(eta(6)-C(6)H(5)X){PCyp(2)(eta(2)-C(5)H(7))}][BAr(4)(F)] (X = H, F) which contain a hybrid phosphine-alkene ligand. These complexes are formed alongside another product (5-20% yield) that has been identified as [Ir(eta(2):eta(2)-C(8)H(12)){PCyp(2)(eta(2)-C(5)H(7))}][BAr(4)(F)], which can be prepared in high yield by an alternative, and slightly modified, route. This complex is with a minor isomer that has been tentatively identified as [Ir(eta(2):eta(3)-C(8)H(11))(H){PCyp(2)(eta(2)-C(5)H(7))}][BAr(4)(F)], which results from allylic C-H activation of cyclooctadiene. Addition of H(2) to [Ir(eta(2):eta(2)-C(8)H(12)){PCyp(2)(eta(2)-C(5)H(7))}][BAr(4)(F)] and its isomer in arene solvent (C(6)H(5)X, X = F, H) forms the dihydrido eta(6)-arene Ir(III) complexes [Ir(H)(2)eta(6)-C(6)H(5)X)(PCyp(3))][BAr(4)(F)]. In contrast, hydrogenation in CH(2)Cl(2) alone results in the formation of [Ir(H)(2)(PCyp(3))eta(6)-(C(3)H(3))(2)][BAr(3)(F)] in which the [BAr(4)(F)](-) anion is now acting as a ligand through one of its aryl rings. The fluorobenzene complex [Ir(H)(2)eta(6)-C(6)H(5)F)(PCyp(3))][BAr(4)(F)] can be cleanly converted to [Ir(eta(6)-C(6)H(5)F){PCyp(2(eta)(2)-C(5)H(7))}]][BAr(4)(F)] by addition of the hydrogen acceptor tert-butylethene (tbe). (C) 2009 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):	Phosphine, Alkenes, Iridium, Dehydrogenation, Anions
Journal or Publication Title:	Inorganica Chimica Acta
Publisher:	Elsevier Science SA
ISSN:	0020-1693
Date:	15 February 2010
Volume:	Vol.363
Number:	No.3
Page Range:	pp. 574-580
Identification Number:	10.1016/j.ica.2009.03.004
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
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URI:	http://wrap.warwick.ac.uk/id/eprint/40523

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