C-metalated diazoalkane complexes of platinum based on PCP- And PCN-type ligands

Elena Poverenov, Gregory Leitus, Linda J.W. Shimon, David Milstein

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

A series of the first C-metalated diazoalkane complexes of Pt, based on pincer-type PCN and PCP ligands (PCP = C6)H3[CH 2P(iPr)2]2) PCN = C2H 3[CH2P(tBu)2](CH2) 2N(CH3)2), with the general formula (PCX)Pt[C(N2)R] (2, X = N, R = Ph; 3, X = N, R = SiMe3; 5, X = P, R = Ph) were prepared via direct nucleophilic attack of RCN 2-Li+ at the metal center. These remarkably stable complexes were characterized by 1H, 31P{ 1H}, and 13C NMR and IR spectroscopy. Complex 2 was also characterized by single-crystal X-ray crystallography. Reactions of the C-metalated diazoalkane Pt complexes with Cu(I) (reported to catalyze decomposition of diazoalkanes) were strongly influenced by the nature of the pincer ligand. Bimolecular coupling to generate diphenylacetylene and (PCP)Pt-OTf (6) was observed in the case of the rigid PCP-based complex 5, while the hemilabile PCN-based complex 2 was converted to an ylide-bridged dimeric structure, the formation of which was promoted by the decoordination of the ligand amine arm. In addition, formation of the stable metalsubstituted azine-type binuclear complex 10, generated by reaction of 2 with Rh 2(OAc)4, is described.

Original languageEnglish
Pages (from-to)5937-5944
Number of pages8
JournalOrganometallics
Volume24
Issue number24
DOIs
Publication statusPublished - Nov 21 2005

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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