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-Benzenedi

详细信息    查看全文

• 作者：Allan J. Canty ; Jim Patel ; Thomas Rodemann ; John H. Ryan ; Brian W. Skelton ; and Allan H. White
• 刊名：Organometallics
• 出版年：2004
• 出版时间：July 5, 2004
• 年：2004
• 卷：23
• 期：14
• 页码：3466 - 3473
• 全文大小：129K
• 年卷期：v.23,no.14(July 5, 2004)
• ISSN：1520-6041

文摘

Diphenyliodine(III) triflate is able to transfer Ph⁺ to Pd(II) and Pt(II) with cleavage of aphenyl-iodine bond and formation of metal(IV) species, leading to the first identified transferof Ph⁺ to Pd(II) from an aryl-halogen bond, and, for platinum, a methodology providing afacile route to dimethyl(aryl)platinum(IV) and 1,4-arenediyl-bridged Pt(IV) species and thefirst archetypal triarylplatinum(IV) complex. Thus, [IPh₂][OTf] reacts with PtMe₂(bpy) (bpy= 2,2'-bipyridine) at -50 mages/entities/deg.gif">C to form iodobenzene and the Pt(IV) complex trans-Pt^IV(OTf)Me₂Ph(N~N) (1b) (Ph trans to OTf), and on addition of NaI, the species PtIMe₂Ph(bpy) (2a (Phcis to I) and 2b (Ph trans to I) in 2:1 ratio) may be isolated at -20 mages/entities/deg.gif">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 ofhalide ion gives trans-PtI(C₄H₈)Ph(bpy) (5b) and a 1:3 ratio of cis and trans isomers forPdI(C₄H₈)Ph(bpy) (6a, 6b) and PdCl(C₄H₈)Ph(bpy) (7a, 7b). Complex 5b isomerizes to forma 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], followedby 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-arenediylcomplex trans-1,4-{PtIMe₂(bpy)}₂C₆H₄ (9b). Diphenyl{di(tert-butyl)-2,2'-bipyridine}platinum(II) reacts with [IPh₂][OTf] at 25 mages/entities/deg.gif">C over 2 days to form the triphenylplatinum(IV) complexPt(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) revealdistorted 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 witha complex array of weak interactions, and the cations have C-I-C angles close to 90mages/entities/deg.gif">.