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Journal of Cluster Science

, Volume 9, Issue 2, pp 165–184 | Cite as

Properties of a New 58-Electron Butterfly [Pt42-dpam)32-CO)31-dpam)]2+ Cluster

  • Tianle Zhang
  • Marc Drouin
  • Pierre D. Harvey
Article

Abstract

A new organometallic cluster [Pt42-dpam)32-CO)31-dpam)] X2 (X=CF3CO 2 - ; 4a) was prepared from a reaction between Pt(dpam)(CF3CO2)2 and CO in a methanol (water mixture). The PF 6 - salt 4b is obtained from an anion exchange with NH4PF6 in methanol. Dark red crystals suitable for X-ray crystallography (X=PF 6 - ) revealed the commonly encountered butterfly structure for a 58-electron Pt cluster (angle between the two Pt3 planes =95.36(8)°, nonbonding Pt...Pt distance =3.094(1) Å). The structure consists of two edge sharing Pt3 triangles, a small one 'Pt32-dpam) 3 2+ and a larger one “Pt32-CO)3(L)3” where L=As group. The Extended Huckel Molecular Orbital calculations (EHMO) have been rationalized from interactions of two L and PtL 2 2+ fragments onto the planar triangular Pt32-CO)3L3 cluster (L = AsH3). The compound is luminescent at 77 K with a structureless band located at 690 nm (τe=3.2 ±0.2μs). Finally, the 1H NMR spectra are interpreted, particularly with respect to fluxionality and presence of two isomers. X-ray data for 4b: orthorhombic, C c2a, a=26.320(9), b=27.613(6), c=28.891(4) Å, V=20998(9) Å3, Z=4, D(calc.)=1.925 Mg/m3.

Platinum electronic spectra luminescence 

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Copyright information

© Plenum Publishing Corporation 1998

Authors and Affiliations

  • Tianle Zhang
    • 1
  • Marc Drouin
    • 2
  • Pierre D. Harvey
    • 1
  1. 1.Département de ChimieUniversité de Sherbrooke, SherbrookeQuébecCanada
  2. 2.Laboratoire de Chimie StructuraleCanada

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