Synthesis and crystal structure of an open capsule-type octanuclear heterometallic sulfide cluster with a linked incomplete double cubane framework without an intramolecular inversion center

Bunsho Kure, Seiji Ogo, Daisuke Inoki, Hidetaka Nakai, Kiyoshi Isobe, Shunichi Fukuzumi

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

An open capsule-type octanuclear heterometallic sulfide cluster without an intramolecular inversion center [Ru(η6-C6Me 6){P(OMe)3}{MoO(μ3-S)3}(Cul) 2]2 (5) has been synthesized for the first time by stepwise connection of three mononuclear building blocks, i.e., (i) [RuCl 26-C6Me6){P(OMe)3}] (1a) as an octahedral terminal building block to control the direction of cluster expansion, (ii) [MoOS3]2- as a tetrahedral polydentate building block owing to the strong coordination ability of the S atoms, and (iii) a Cul building block to form a trigonal planar (μ-S) 2Cul unit or to form a linkage unit of two incomplete cubane-type octanuclear frameworks. The stepwise connection was made in the following order: [RuCl26-C6Me6){P(OMe) 3}] (1a, mononuclear) → [Ru(η6-C 6Me6){P(OMe)3}{MoOS(μ2-S) 2}] (2a, dinuclear) → [Ru(η6-C6Me 6){P(OMe)3}{MoO-(μ2-S)23-S)}Cul] (3a, butterfly-type trinuclear) → [Ru(η 6-C6Me6){P(OMe)3} {MoO(μ3-S)3}(Cul)2]2 (5). When P(OMe)3 was replaced by P(OEt)3, which is more bulky than P(OMe)3, in the starting ruthenium building block [RuCl 26-C6Me6){P(OEt)3}] (1b, mononuclear), only the tetranuclear incomplete single cubane cluster [Ru(η6-C6Me6){P(OEt)3} {MoO(μ3-S)3}(Cul)2] (6) was generated, owing to the steric effect of P(OEt)3.

Original languageEnglish
Pages (from-to)14366-14374
Number of pages9
JournalJournal of the American Chemical Society
Volume127
Issue number41
DOIs
Publication statusPublished - Oct 19 2005
Externally publishedYes

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Plant expansion
Butterflies
Ruthenium
Sulfides
Capsules
Crystal structure
Atoms
Direction compound

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Synthesis and crystal structure of an open capsule-type octanuclear heterometallic sulfide cluster with a linked incomplete double cubane framework without an intramolecular inversion center. / Kure, Bunsho; Ogo, Seiji; Inoki, Daisuke; Nakai, Hidetaka; Isobe, Kiyoshi; Fukuzumi, Shunichi.

In: Journal of the American Chemical Society, Vol. 127, No. 41, 19.10.2005, p. 14366-14374.

Research output: Contribution to journalArticle

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title = "Synthesis and crystal structure of an open capsule-type octanuclear heterometallic sulfide cluster with a linked incomplete double cubane framework without an intramolecular inversion center",
abstract = "An open capsule-type octanuclear heterometallic sulfide cluster without an intramolecular inversion center [Ru(η6-C6Me 6){P(OMe)3}{MoO(μ3-S)3}(Cul) 2]2 (5) has been synthesized for the first time by stepwise connection of three mononuclear building blocks, i.e., (i) [RuCl 2(η6-C6Me6){P(OMe)3}] (1a) as an octahedral terminal building block to control the direction of cluster expansion, (ii) [MoOS3]2- as a tetrahedral polydentate building block owing to the strong coordination ability of the S atoms, and (iii) a Cul building block to form a trigonal planar (μ-S) 2Cul unit or to form a linkage unit of two incomplete cubane-type octanuclear frameworks. The stepwise connection was made in the following order: [RuCl2(η6-C6Me6){P(OMe) 3}] (1a, mononuclear) → [Ru(η6-C 6Me6){P(OMe)3}{MoOS(μ2-S) 2}] (2a, dinuclear) → [Ru(η6-C6Me 6){P(OMe)3}{MoO-(μ2-S)2(μ 3-S)}Cul] (3a, butterfly-type trinuclear) → [Ru(η 6-C6Me6){P(OMe)3} {MoO(μ3-S)3}(Cul)2]2 (5). When P(OMe)3 was replaced by P(OEt)3, which is more bulky than P(OMe)3, in the starting ruthenium building block [RuCl 2(η6-C6Me6){P(OEt)3}] (1b, mononuclear), only the tetranuclear incomplete single cubane cluster [Ru(η6-C6Me6){P(OEt)3} {MoO(μ3-S)3}(Cul)2] (6) was generated, owing to the steric effect of P(OEt)3.",
author = "Bunsho Kure and Seiji Ogo and Daisuke Inoki and Hidetaka Nakai and Kiyoshi Isobe and Shunichi Fukuzumi",
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T1 - Synthesis and crystal structure of an open capsule-type octanuclear heterometallic sulfide cluster with a linked incomplete double cubane framework without an intramolecular inversion center

AU - Kure, Bunsho

AU - Ogo, Seiji

AU - Inoki, Daisuke

AU - Nakai, Hidetaka

AU - Isobe, Kiyoshi

AU - Fukuzumi, Shunichi

PY - 2005/10/19

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N2 - An open capsule-type octanuclear heterometallic sulfide cluster without an intramolecular inversion center [Ru(η6-C6Me 6){P(OMe)3}{MoO(μ3-S)3}(Cul) 2]2 (5) has been synthesized for the first time by stepwise connection of three mononuclear building blocks, i.e., (i) [RuCl 2(η6-C6Me6){P(OMe)3}] (1a) as an octahedral terminal building block to control the direction of cluster expansion, (ii) [MoOS3]2- as a tetrahedral polydentate building block owing to the strong coordination ability of the S atoms, and (iii) a Cul building block to form a trigonal planar (μ-S) 2Cul unit or to form a linkage unit of two incomplete cubane-type octanuclear frameworks. The stepwise connection was made in the following order: [RuCl2(η6-C6Me6){P(OMe) 3}] (1a, mononuclear) → [Ru(η6-C 6Me6){P(OMe)3}{MoOS(μ2-S) 2}] (2a, dinuclear) → [Ru(η6-C6Me 6){P(OMe)3}{MoO-(μ2-S)2(μ 3-S)}Cul] (3a, butterfly-type trinuclear) → [Ru(η 6-C6Me6){P(OMe)3} {MoO(μ3-S)3}(Cul)2]2 (5). When P(OMe)3 was replaced by P(OEt)3, which is more bulky than P(OMe)3, in the starting ruthenium building block [RuCl 2(η6-C6Me6){P(OEt)3}] (1b, mononuclear), only the tetranuclear incomplete single cubane cluster [Ru(η6-C6Me6){P(OEt)3} {MoO(μ3-S)3}(Cul)2] (6) was generated, owing to the steric effect of P(OEt)3.

AB - An open capsule-type octanuclear heterometallic sulfide cluster without an intramolecular inversion center [Ru(η6-C6Me 6){P(OMe)3}{MoO(μ3-S)3}(Cul) 2]2 (5) has been synthesized for the first time by stepwise connection of three mononuclear building blocks, i.e., (i) [RuCl 2(η6-C6Me6){P(OMe)3}] (1a) as an octahedral terminal building block to control the direction of cluster expansion, (ii) [MoOS3]2- as a tetrahedral polydentate building block owing to the strong coordination ability of the S atoms, and (iii) a Cul building block to form a trigonal planar (μ-S) 2Cul unit or to form a linkage unit of two incomplete cubane-type octanuclear frameworks. The stepwise connection was made in the following order: [RuCl2(η6-C6Me6){P(OMe) 3}] (1a, mononuclear) → [Ru(η6-C 6Me6){P(OMe)3}{MoOS(μ2-S) 2}] (2a, dinuclear) → [Ru(η6-C6Me 6){P(OMe)3}{MoO-(μ2-S)2(μ 3-S)}Cul] (3a, butterfly-type trinuclear) → [Ru(η 6-C6Me6){P(OMe)3} {MoO(μ3-S)3}(Cul)2]2 (5). When P(OMe)3 was replaced by P(OEt)3, which is more bulky than P(OMe)3, in the starting ruthenium building block [RuCl 2(η6-C6Me6){P(OEt)3}] (1b, mononuclear), only the tetranuclear incomplete single cubane cluster [Ru(η6-C6Me6){P(OEt)3} {MoO(μ3-S)3}(Cul)2] (6) was generated, owing to the steric effect of P(OEt)3.

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