Synthesis and reactivities of Ir2Ru heterobimetallic sulfido clusters derived from a hydrogensulfido-bridged diiridium complex

Takuya Kochi, Yasuo Nomura, Zhen Tang, Youichi Ishii, Yasushi Mizobe, Masanobu Hidai

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Abstract

The hydrogensulfido-bridged diiridium complex [ClCp*Ir(μ-SH)2IrCp*Cl] reacted with [RuH2(PPh3)4] to give a mixed-metal trinuclear cluster with an Ir2Ru(μ3-S)2 core [(Cp*Ir)23-S)2RuCl 2(PPh3)] 2, which was further converted into the cationic diphosphine derivatives [(Cp*Ir)23-S)2RuCl(L)]Cl (L = dppe = Ph2PCH2CH2PPh2 3 or depe = Et2PCH2CH2PEt2 4). The reaction of cluster 3 with Me2CuLi followed by anion metathesis with KPF6 afforded the cationic methyl cluster [(Cp*Ir)23-S)2RuMe(dppe)][PF 6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formation of [(Cp*Ir){(η4-C5Me5CHCl 2)Ir}(μ3-S)2RuCl(dppe)] 6, in which one of the Cp* ligands was alkylated by CHCl2Li to form an η4-diene. Clusters 3 and 4 were also transformed into the dihydrido clusters [(Cp*Ir)23-S)2(μ-H) 2Ru(L)] (L = dppe 7 or depe 8) by the reaction with NaBH4. On the other hand, cluster 2 was converted into the carbonyl cluster [(Cp*Ir)23-S)2RuCl(CO)(PPh 3)]Cl 9, the isocyanide clusters [(Cp*Ir)23-S)2RuCl(CNXy)(PPh 3)]Cl 10 (Xy = 2,6-C6H3Me2) and [(Cp*Ir)23-S)2Ru(CNXy) 2(PPh3)][BPh4]2 11 and the co-ordinatively unsaturated thiolato clusters [(Cp*Ir)23-S)2Ru(SAr)2] (Ar = 2,4,6-C6H2Pri3 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular structures of [(Cp*Ir)23-S)2RuCl(depe)][BPh 4] 4′, 5′CH2Cl2, 6, 7 and 12·2C6H6 were established by X-ray diffraction studies.

Original languageEnglish
Pages (from-to)2575-2582
Number of pages8
JournalJournal of the Chemical Society - Dalton Transactions
Issue number15
Publication statusPublished - 1999 Aug 7
Externally publishedYes

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Carbon Monoxide
Cyanides
Molecular structure
Anions
Metals
Ligands
Derivatives
X ray diffraction

ASJC Scopus subject areas

  • Inorganic Chemistry

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Synthesis and reactivities of Ir2Ru heterobimetallic sulfido clusters derived from a hydrogensulfido-bridged diiridium complex. / Kochi, Takuya; Nomura, Yasuo; Tang, Zhen; Ishii, Youichi; Mizobe, Yasushi; Hidai, Masanobu.

In: Journal of the Chemical Society - Dalton Transactions, No. 15, 07.08.1999, p. 2575-2582.

Research output: Contribution to journalArticle

@article{b4a95f2260f94d1cb297a50cd7ae2b45,
title = "Synthesis and reactivities of Ir2Ru heterobimetallic sulfido clusters derived from a hydrogensulfido-bridged diiridium complex",
abstract = "The hydrogensulfido-bridged diiridium complex [ClCp*Ir(μ-SH)2IrCp*Cl] reacted with [RuH2(PPh3)4] to give a mixed-metal trinuclear cluster with an Ir2Ru(μ3-S)2 core [(Cp*Ir)2(μ3-S)2RuCl 2(PPh3)] 2, which was further converted into the cationic diphosphine derivatives [(Cp*Ir)2(μ3-S)2RuCl(L)]Cl (L = dppe = Ph2PCH2CH2PPh2 3 or depe = Et2PCH2CH2PEt2 4). The reaction of cluster 3 with Me2CuLi followed by anion metathesis with KPF6 afforded the cationic methyl cluster [(Cp*Ir)2(μ3-S)2RuMe(dppe)][PF 6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formation of [(Cp*Ir){(η4-C5Me5CHCl 2)Ir}(μ3-S)2RuCl(dppe)] 6, in which one of the Cp* ligands was alkylated by CHCl2Li to form an η4-diene. Clusters 3 and 4 were also transformed into the dihydrido clusters [(Cp*Ir)2(μ3-S)2(μ-H) 2Ru(L)] (L = dppe 7 or depe 8) by the reaction with NaBH4. On the other hand, cluster 2 was converted into the carbonyl cluster [(Cp*Ir)2(μ3-S)2RuCl(CO)(PPh 3)]Cl 9, the isocyanide clusters [(Cp*Ir)2(μ3-S)2RuCl(CNXy)(PPh 3)]Cl 10 (Xy = 2,6-C6H3Me2) and [(Cp*Ir)2(μ3-S)2Ru(CNXy) 2(PPh3)][BPh4]2 11 and the co-ordinatively unsaturated thiolato clusters [(Cp*Ir)2(μ3-S)2Ru(SAr)2] (Ar = 2,4,6-C6H2Pri3 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular structures of [(Cp*Ir)2(μ3-S)2RuCl(depe)][BPh 4] 4′, 5′CH2Cl2, 6, 7 and 12·2C6H6 were established by X-ray diffraction studies.",
author = "Takuya Kochi and Yasuo Nomura and Zhen Tang and Youichi Ishii and Yasushi Mizobe and Masanobu Hidai",
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T1 - Synthesis and reactivities of Ir2Ru heterobimetallic sulfido clusters derived from a hydrogensulfido-bridged diiridium complex

AU - Kochi, Takuya

AU - Nomura, Yasuo

AU - Tang, Zhen

AU - Ishii, Youichi

AU - Mizobe, Yasushi

AU - Hidai, Masanobu

PY - 1999/8/7

Y1 - 1999/8/7

N2 - The hydrogensulfido-bridged diiridium complex [ClCp*Ir(μ-SH)2IrCp*Cl] reacted with [RuH2(PPh3)4] to give a mixed-metal trinuclear cluster with an Ir2Ru(μ3-S)2 core [(Cp*Ir)2(μ3-S)2RuCl 2(PPh3)] 2, which was further converted into the cationic diphosphine derivatives [(Cp*Ir)2(μ3-S)2RuCl(L)]Cl (L = dppe = Ph2PCH2CH2PPh2 3 or depe = Et2PCH2CH2PEt2 4). The reaction of cluster 3 with Me2CuLi followed by anion metathesis with KPF6 afforded the cationic methyl cluster [(Cp*Ir)2(μ3-S)2RuMe(dppe)][PF 6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formation of [(Cp*Ir){(η4-C5Me5CHCl 2)Ir}(μ3-S)2RuCl(dppe)] 6, in which one of the Cp* ligands was alkylated by CHCl2Li to form an η4-diene. Clusters 3 and 4 were also transformed into the dihydrido clusters [(Cp*Ir)2(μ3-S)2(μ-H) 2Ru(L)] (L = dppe 7 or depe 8) by the reaction with NaBH4. On the other hand, cluster 2 was converted into the carbonyl cluster [(Cp*Ir)2(μ3-S)2RuCl(CO)(PPh 3)]Cl 9, the isocyanide clusters [(Cp*Ir)2(μ3-S)2RuCl(CNXy)(PPh 3)]Cl 10 (Xy = 2,6-C6H3Me2) and [(Cp*Ir)2(μ3-S)2Ru(CNXy) 2(PPh3)][BPh4]2 11 and the co-ordinatively unsaturated thiolato clusters [(Cp*Ir)2(μ3-S)2Ru(SAr)2] (Ar = 2,4,6-C6H2Pri3 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular structures of [(Cp*Ir)2(μ3-S)2RuCl(depe)][BPh 4] 4′, 5′CH2Cl2, 6, 7 and 12·2C6H6 were established by X-ray diffraction studies.

AB - The hydrogensulfido-bridged diiridium complex [ClCp*Ir(μ-SH)2IrCp*Cl] reacted with [RuH2(PPh3)4] to give a mixed-metal trinuclear cluster with an Ir2Ru(μ3-S)2 core [(Cp*Ir)2(μ3-S)2RuCl 2(PPh3)] 2, which was further converted into the cationic diphosphine derivatives [(Cp*Ir)2(μ3-S)2RuCl(L)]Cl (L = dppe = Ph2PCH2CH2PPh2 3 or depe = Et2PCH2CH2PEt2 4). The reaction of cluster 3 with Me2CuLi followed by anion metathesis with KPF6 afforded the cationic methyl cluster [(Cp*Ir)2(μ3-S)2RuMe(dppe)][PF 6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formation of [(Cp*Ir){(η4-C5Me5CHCl 2)Ir}(μ3-S)2RuCl(dppe)] 6, in which one of the Cp* ligands was alkylated by CHCl2Li to form an η4-diene. Clusters 3 and 4 were also transformed into the dihydrido clusters [(Cp*Ir)2(μ3-S)2(μ-H) 2Ru(L)] (L = dppe 7 or depe 8) by the reaction with NaBH4. On the other hand, cluster 2 was converted into the carbonyl cluster [(Cp*Ir)2(μ3-S)2RuCl(CO)(PPh 3)]Cl 9, the isocyanide clusters [(Cp*Ir)2(μ3-S)2RuCl(CNXy)(PPh 3)]Cl 10 (Xy = 2,6-C6H3Me2) and [(Cp*Ir)2(μ3-S)2Ru(CNXy) 2(PPh3)][BPh4]2 11 and the co-ordinatively unsaturated thiolato clusters [(Cp*Ir)2(μ3-S)2Ru(SAr)2] (Ar = 2,4,6-C6H2Pri3 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular structures of [(Cp*Ir)2(μ3-S)2RuCl(depe)][BPh 4] 4′, 5′CH2Cl2, 6, 7 and 12·2C6H6 were established by X-ray diffraction studies.

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