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DOI: 10.1039/A902999K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2575-2582

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

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

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)2RuCl2(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)][PF6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formation of [(Cp*Ir){(η4-C5Me5CHCl2)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)(PPh3)]Cl 9, the isocyanide clusters [(Cp*Ir)2(µ3-S)2RuCl(CNXy)(PPh3)]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)][BPh4] 4′, 5·CH2Cl2, 6, 7 and 12·2C6H6 were established by X-ray diffraction studies.

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