Triangular platinum(II) cluster complexes and cluster core transformation from square-planar to triangular type

Tadashi Yamaguchi, Nozomu Nishimura, Ken Ichi Shirakura, Tasuku Ito

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8 Citations (Scopus)

Abstract

Reactions of [Pt(II)4(μCH3COO)8] (1) with dioximes or with N,N'- dimethylethylenediamine induced a cluster core transformation from a square planar to a triangular type to afford Pt(II)3 clusters. Three of these clusters have been characterized by X-ray analyses. The structure of the Pt(II)3 cluster core is an approximate or regular isosceles triangle, two equidistant edges (2.51-2.56 Å) being somewhat shorter than the other (2.59- 2.61 Å). The cluster core transformation proceeds through the substitution of the in-plane acetate ligands in 1 by incoming ligands followed by the removal of one Pt atom from the tetranuclear cluster core. An intermediate of the cluster core transformation, [{Pt4(CH3COO)4(dmgH)2(dmgH2)}2(μ- dmgH2)], was structurally characterized. It is a dimer of tetranuclear Pt(II) complex and consists of a triangular cluster unit and a mononuclear unit with square planar geometry. EHMO study and large 1J(Pt-Pt) values of ca. 8000 Hz suggest the stability of the triangular Pt(II)3 cluster core and the existence of strong Pt-Pt bonds. Ligands in the Pt(II)3 cluster plane are labilized by trans effect of Pt-Pt bonds, although intramolecular hydrogen bonds reduce the lability. On the other hand, out-of-plane acetate ligands are substitution inert.

Original languageEnglish
Pages (from-to)775-784
Number of pages10
JournalBulletin of the Chemical Society of Japan
Volume73
Issue number4
DOIs
Publication statusPublished - 2000 Apr 1

ASJC Scopus subject areas

  • Chemistry(all)

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