Platinum-Assisted C-C Bond Formation. Synthesis of Platinum Imidoyl Phosphorus Ylide Complexes and the First Crystal Structure of an Imidoyl Phosphorus Ylide Complex

José Vicente*, María Teresa Chicote, María Cristina Lagunas, Peter G. Jones

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

40 Citations (Scopus)

Abstract

[To3PCH2(Py-2)]Cl ([1]+Cl, To = C6H4Me-4, Py = pyridine) reacts with PtCl2 (1:1) to give [PtCl3{Py{CH2-PTo3}-2}] (2). This complex reacts with various bases, but complex mixtures, which we were unable to separate, are obtained. However, the reaction between [1]+Cl, trans-[PtCl2(NCPh)2], and Na2CO3 after refluxing gives mixtures from which it is possible to isolate and characterize the complex cis-[PtCl2{NH=C(Ph)C(=PTo3)(Py-2)-N, N′}] (3). Similarly, starting from the trans-[PtCl2(NCMe)2] complex, cis-[PtCl2{NH=C(Me)C(=PTo3)(Py-2)-N, N′}] (4) is obtained. These are the first imidoyl phosphorus ylide complexes of platinum. The crystal structures of 3-CH2Cl2 and 3–3CHCl3 were determined [3>CH2Cl2: C35H33Cl4N2PPt, triclinic, P1, 173(2) K, a = 11.367(6) Å, b= 14.252(6) Å, c = 14.532(7) Å, a = 60.87(3)°, β = 74.62(4)°, γ = 73.17(4)°. 3·3CHCl3: C37H34Cl11N2PPt, triclinic, P1, 143(2) K, a = 11.257(3) Å, b= 12.132(4) Å, c = 16.921(5) Å, a = 105.90(2)°, β = 105.75(2)°, γ = 90.14(2)°, Z = 2]. These are the first crystal structures of imidoyl phosphorus ylide complexes. The Pt-Cl bond distances are significantly different, showing the greater trans influence of imino group compared to the pyridyl group. The double-bond character of the N(1)-C(2) and P-C(1) bonds is reduced via conjugation through the C(1)-C(2) bond.

Original languageEnglish
Pages (from-to)5441-5445
Number of pages5
JournalInorganic Chemistry
Volume34
Issue number22
DOIs
Publication statusPublished - 01 Oct 1995
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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