A Comparative Study of Isostructural Palladium and Platinum Methyl Complexes. The Structures of cis-Dimethylbis(diphenylmethylphosphine)palladium(II) and cis-Dlmethylbis(diphenylmethylphosphine)platlnum(II)

Jean M. Wisner, Tadeusz J. Bartczak, James A. Ibers

Research output: Contribution to journalArticle

64 Scopus citations

Abstract

The structures of cis-dimethylbis(diphenylmethylphosphine)palIadium(II) and cis-dimethylbis(di-phenylmethylphosphine)platinum(II) have been determined crystallographically at -162 °C. The palladium complex crystallizes from acetone in the monoclinic space group with four formula units in a unit cell of dimensions a =8.882 (3) A, b = 26.500 (7) A, c = 11.168 (4) A, and ß= 108.27 (4)°. The structure has been refined to an R index on F2of 0.038 for 4799 observations and 280 variables. The platinum congener crystallizes from a benzene/ethanol mixture with four molecules in the space group of the monoclinic system in a cell of dimensions a =8.859 (4) A, b = 26.302 (10) A, c = 11.215 (5) A, and ß = 108.60 (2)°. The Pt structure has been refined to an R index on F2 of 0.078 for 7678 observations and 280 variables. Both complexes possess slightly distorted square-planar geometry: P(l)-Pd-P(2) = 98.24 (4)°, P(l)-Pt-P(2) = 97.75 (6)°, C(l)-Pd-C(2) = 82.9 (1)°, and C(l)-Pt-C(2) = 81.9 (2)°. Some important bond distances are as follows: Pd-C = 2.089 (3), 2.090 (3) A; Pt-C = 2.122 (6), 2.119 (5) A; Pd-P = 2.326 (1), 2.321 (1) A; Pt-P = 2.285 (2), 2.284 (2) A. Comparison of the two structures shows a lengthening of the M-C bonds and a concomitant shortening of the M-P bonds when the central metal is changed from palladium to platinum. These structural data are correlated with differences in reactivity. In addition, sets of isostructural compounds in other metal triads are surveyed for analogous trends in bond distances.

Original languageEnglish (US)
Pages (from-to)2044-2050
Number of pages7
JournalOrganometallics
Volume5
Issue number10
DOIs
StatePublished - Jan 1 1986

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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