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Alkyl dehydrogenation in iridium tri-cyclopentyl phosphines
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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. doi:10.1016/j.ica.2009.03.004 ISSN 0020-1693.
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Official URL: http://dx.doi.org/10.1016/j.ica.2009.03.004
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 | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Divisions: | Faculty of Science, Engineering and Medicine > 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 | ||||
Official Date: | 15 February 2010 | ||||
Dates: |
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Volume: | Vol.363 | ||||
Number: | No.3 | ||||
Page Range: | pp. 574-580 | ||||
DOI: | 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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