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Reactivity of Diaryliodine(III) Triflates toward Palladium(II) and Platinum(II): Reactions of C(sp²)−I Bonds to Form Arylmetal(IV) Complexes; Access to Dialkyl(aryl)metal(IV), 1,4-Benzenediyl-Bridged Platinum(IV), and Triphenylplatinum(IV) Species; and Structural Studies of Platinum(IV) Complexes

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Allan J. Canty,*^† Jim Patel,^† Thomas Rodemann,^† John H. Ryan,^† Brian W. Skelton,^‡ and Allan H. White^‡

School of Chemistry, University of Tasmania, Hobart, Tasmania 7001, Australia, and School of Biomedical & Chemical Sciences, University of Western Australia, Crawley, Western Australia 6009, Australia

Organometallics, 2004, 23 (14), pp 3466–3473

DOI: 10.1021/om040023c

Publication Date (Web): June 4, 2004

Section:

Organometallic and Organometalloidal Compounds

Abstract

Diphenyliodine(III) triflate is able to transfer Ph⁺ to Pd(II) and Pt(II) with cleavage of a phenyl−iodine bond and formation of metal(IV) species, leading to the first identified transfer of Ph⁺ to Pd(II) from an aryl−halogen bond, and, for platinum, a methodology providing a facile route to dimethyl(aryl)platinum(IV) and 1,4-arenediyl-bridged Pt(IV) species and the first archetypal triarylplatinum(IV) complex. Thus, [IPh₂][OTf] reacts with PtMe₂(bpy) (bpy = 2,2‘-bipyridine) at −50 °C to form iodobenzene and the Pt(IV) complex trans-Pt^IV(OTf)Me₂Ph(NN) (1b) (Ph trans to OTf), and on addition of NaI, the species PtIMe₂Ph(bpy) (2a (Ph cis to I) and 2b (Ph trans to I) in 2:1 ratio) may be isolated at −20 °C. Similarly, metalla(II)cyclopentane complexes M(C₄H₈)(bpy) react with [IPh₂][OTf] to form trans-Pt(OTf)(C₄H₈)Ph(bpy) (3b) and a 1:1 ratio of cis- (4a) and trans-Pd(OTf)(C₄H₈)Ph(bpy) (4b); addition of halide ion gives trans-PtI(C₄H₈)Ph(bpy) (5b) and a 1:3 ratio of cis and trans isomers for PdI(C₄H₈)Ph(bpy) (6a, 6b) and PdCl(C₄H₈)Ph(bpy) (7a, 7b). Complex 5b isomerizes to form a 2:1 mixture of cis-PtI(C₄H₈)Ph(bpy) (5a) and 5b at ambient temperature in acetone. Dimethyl(2,2‘-bipyridine)palladium(II) reacts with [IPh₂][OTf] to form Pd(OTf)Me₂Ph(bpy), followed by transfer of a methyl group from Pd(IV) to Pd(II), to form trimethylpalladium(IV) species. Dimethyl(2,2‘-bipyridine)platinum(II) reacts with [IPh(C₆H₄-4-I)][OTf], followed by addition of sodium iodide, to form a 1:1 mixture of trans-PtIMe₂Ph(bpy) (2b) and trans-PtIMe₂(C₆H₄-4-I)(bpy) (8b), and with [IPh(C₆H₄-4-IPh)][OTf]₂ to form the 1,4-arenediyl complex trans-1,4-{PtIMe₂(bpy)}₂C₆H₄ (9b). Diphenyl{di(tert-butyl)-2,2‘-bipyridine}platinum(II) reacts with [IPh₂][OTf] at 25 °C over 2 days to form the triphenylplatinum(IV) complex Pt(OTf)Ph₃(Bu^t₂bpy) (10), and addition of iodide ion results in isolation of PtIPh₃(Bu^t₂bpy) (11). Structural studies of trans-PtIMe₂Ph(bpy) (2b) and trans-Pt(C₄H₈)Ph(bpy) (5b) reveal distorted octahedral geometry and the fac-PtC₃ configuration expected for all of the metal(IV) complexes. The compound [IPh(C₆H₄-4-I)][OTf] has two sets of cation−anion pairs with a complex array of weak interactions, and the cations have C−I−C angles close to 90°.

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Published In Issue July 05, 2004
Received February 27, 2004

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Article

Reactivity of Diaryliodine(III) Triflates toward Palladium(II) and Platinum(II): Reactions of C(sp²)−I Bonds to Form Arylmetal(IV) Complexes; Access to Dialkyl(aryl)metal(IV), 1,4-Benzenediyl-Bridged Platinum(IV), and Triphenylplatinum(IV) Species; and Structural Studies of Platinum(IV) Complexes

Abstract

Citing Articles

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