Reactions of Perfluoroalkyl Iodides with M(C5H5)(CO)(PMe3) [M = Rh, Ir]; Evidence for Direct Fluoroalkylation at a CO Ligand

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• 作者：Cheryl J. Bourgeois ; Russell P. Hughes ; Trang L. Husebo ; Jeremy M. Smith ; Ilia M Guzei ; Louise M. Liable-Sands ; Lev N. Zakharov ; and Arnold L. Rheingold
• 刊名：Organometallics
• 出版年：2005
• 出版时间：December 19, 2005
• 年：2005
• 卷：24
• 期：26
• 页码：6431 - 6439
• 全文大小：250K
• 年卷期：v.24,no.26(December 19, 2005)
• ISSN：1520-6041

文摘

While reaction of n-C₃F₇I with CpRh(PMe₃)(CO) gives the expected product of oxidativeaddition, CpRh(PMe₃)(ⁿC₃F₇)(I), the analogous reaction of iso-C₃F₇I affords a mixture of CpRh(PMe₃)(CF(CF₃)₂)(I) and the perfluoroacyl complex CpRh(PMe₃)(COCF(CF₃)₂)(I). The lattercompound is not formed from the former by a migratory insertion reaction. In furthercontrast, low-temperature reaction of CpIr(CO)(PMe₃) with n-C₃F₇I gives the ionic complex[CpIr(CO)(PMe₃)(ⁿC₃F₇)]⁺I^-, which is inert to thermal substitution; treatment with N-methylmorpholine-N-oxide (NMO) results in CO oxidation and iodide coordination to giveCpIr(PMe₃)(ⁿC₃F₇)(I). The same reaction at room temperature affords a mixture of fourproducts, including small amounts of [CpIr(CO)(PMe₃)(ⁿC₃F₇)]⁺I^- and CpIr(PMe₃)(ⁿC₃F₇)(I); the major components are the perfluoroacyl complex CpIr(PMe₃)(COⁿC₃F₇)(I) and theperfluoroacyl(perfluoroalkyl) complex CpIr(PMe₃)(COⁿC₃F₇)(ⁿC₃F₇). Crystallographic structure determinations of all these molecules are reported, and a mechanism involving directfluoroalkylation at CO is proposed.