Sterically hindered metal alkenyls. Part 1. Synthesis, reactions, and crystal and molecular structures of some palladium and platinum σ-alkenyls

Cardin, C. J. ORCID: https://orcid.org/0000-0002-2556-9995, Cardin, D. J., Parge, H. E. and Sullivan, A. C. (1986) Sterically hindered metal alkenyls. Part 1. Synthesis, reactions, and crystal and molecular structures of some palladium and platinum σ-alkenyls. Journal of the Chemical Society, Dalton Transactions (11). pp. 2315-2320. ISSN 1364-5447 doi: 10.1039/DT9860002315

Abstract/Summary

The compounds trans-[PtBr{C(C10H15)CH2}(PEt3)2](1)(C10H15= adamant-1-yl), trans-[MBr{C(C10H7)CMe2}(PEt3)2][M = Pd (2) or Pt (3); C10H7= naphth-1-yl], and trans-[MBr{C(Ph)CMe2}(PEt3)2][M = Pd (4) or Pt (5)] have been prepared from Grignard [for (2) and (3)] or lithium reagents [for (1), (4), and (5)] and appropriate dichlorobis(phosphine)metal derivatives. Full single-crystal X-ray data are reported for (1) and (3), and reveal unusually long Pt–C(sp2) bonds. Insertion reactions into these M–C bonds occur with MeNC [for (1), (3), and (5)], and with CO [for (1) and (3)]; the latter, the first reported insertion into a Pt–C(sp2) bond, occurs under mild conditions as expected for the abnormally long M–C bonds.