Synthesis, structure, and reactivity of new rhodium and iridium complexes, bearing a highly electron-donating PNP system. Iridium-mediated vinylic C-H bond activation

Dominik Hermann, Mark Gandelman, Haim Rozenberg, Linda J W Shimon, David Milstein

Research output: Contribution to journalArticle

113 Citations (Scopus)

Abstract

Reaction of the new highly electron-donating PNP ligand [2,6-bis-(di-tert-butylphosphi-nomethl)pyridine] (1) with [Rh(COE)2Cl]2 (COE = cyclooctene) at room temperature resulted in formation of the neutral Rh(I) complex [Rh(PNP)Cl] (2). Unsaturated cationic complexes [Rh(PNP)(CH3CN)]BF4 (3) and [Rh(PNP)(C2H4)]SO3CF3 (4) were obtained in reaction of 1 with [(COE)2Rh(CH3CN)2]BF4 and [(C2H4)2Rh(THF)2]SO3CF 3, respectively. Upon reaction of the PNP ligand 1 with [Ir(COE)2Cl]2, facile vinylic C-H activation takes place, yielding the hydrido-vinyl complex [ClIr(PNP)(H)(C8H13)] (5). Also, coordination of ligand 1 to the cationic iridium complex [Ir(COD)2]BF4 (COD = cyclooctadiene) in RCN (R = CH3, CH(CH3)2, C(CH3)3) led to iridium insertion into a vinylic C-H bond, resulting in complexes [(RCN)-Ir(PNP)(H)(C8H11)]BF4 (6a-c). The hydrido-vinyl complexes 6a,c readily react with H2 (2 atm) at room temperature, affording the iridium dihydride complexes [(RCN)Ir(PNP)-(H)2]BF4 (R = CH3, C(CH3)3) (7a,b).

Original languageEnglish
Pages (from-to)812-818
Number of pages7
JournalOrganometallics
Volume21
Issue number5
DOIs
Publication statusPublished - Mar 4 2002

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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