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

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

doi:10.1246/bcsj.73.775

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

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

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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 language	English
Pages (from-to)	775-784
Number of pages	10
Journal	Bulletin of the Chemical Society of Japan
Volume	73
Issue number	4
DOIs	https://doi.org/10.1246/bcsj.73.775
Publication status	Published - 2000 Apr 1
Externally published	Yes

ASJC Scopus subject areas

Chemistry(all)

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@article{723e10c6741d4eb78a6713c7d7679c3c,

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

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 {\AA}) being somewhat shorter than the other (2.59- 2.61 {\AA}). 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.",

author = "Tadashi Yamaguchi and Nozomu Nishimura and Shirakura, {Ken Ichi} and Tasuku Ito",

year = "2000",

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doi = "10.1246/bcsj.73.775",

language = "English",

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T1 - Triangular platinum(II) cluster complexes and cluster core transformation from square-planar to triangular type

AU - Yamaguchi, Tadashi

AU - Nishimura, Nozomu

AU - Shirakura, Ken Ichi

AU - Ito, Tasuku

PY - 2000/4/1

Y1 - 2000/4/1

N2 - 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.

AB - 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.

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

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