Pt-NOx Chemistry. Preparation and Structure of trans-Dinitrobis(tri-p-tolylphosphine)platinum(II), Pt(NO2)2(P(p-C6H4CH3)3)2

James A. Kaduk, James A. Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

The structure of trans-dinitrobis(tri-p-tolylphosphine)platinum(II), Pt(NO2)2(P(p-C6H4CH3)3)2, has been determined from three-dimensional x-ray data. The compound was isolated while attempting to grow crystals of Pt(N2O2) (P(p-C6H4CH3)3)2. The complex crystallizes in the space group C2h5-P21/n with two molecules in a unit cell of dimensions a = 11.585 (6) Å, b = 18.387 (9) Å, c = 10.697 (9) Å, and β = 119.30 (4)°. Least-squares refinement of the 106 variables has led to a value of the conventional R index (on F) of 0.043 for the 4735 independent reflections having Fo2> 3σ(Fo2). The complex is a typical square-planar Pt(II) complex. The Pt atom occupies a crystallographic center of symmetry. Important structural parameters include: Pt-P = 2.337 (1) Å, Pt-N = 2.030 (5) Å, N-O(l) = 1.228 (8) Å, N-O(2) = 1.198 (7) Å, N-Pt-P = 88.4 (1)°, N-Pt-P′ = 91.6 (1)°, O(1)-N-O(2) = 121.7 (6)°, Pt-N-O(1) = 118.9 (5)°, Pt-N-G(2) = 119.4 (5)°. The angle between the plane of the nitro ligand and the coordination plane is 75°. The structural results provide no evidence of Pt(II)-NO2π bonding. Several reactions of Pt(N2O2)(PPh3)2 and Pt(0) complexes with nitrogen oxides are described, and the production of trans-Pt(NO2)2(P(p-C6H4CH3)3)2 from Pt(N2O2)(P(p-C6H4CH3)3)2 is rationalized.

Original languageEnglish (US)
Pages (from-to)3278-3282
Number of pages5
JournalInorganic chemistry
Volume16
Issue number12
DOIs
StatePublished - Dec 1 1977

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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