Synthesis and reactivities of Ir_2Ru heterobimetallic sulfido clusters derived from a hydrogensulfido-bridged diiridium complex

摘要

The hydrogensulfido-bridged diiridium complex [ClCp~*Ir(#mu#-SH)_2IrCP~*Cl] reacted with [RuH_2(PPh_3(_4] to give a mixed-metal trinuclear cluster with an Ir_2Ru(#mu#_3-S)_2 core [(Cp~*Ir)_2(#mu#_3-S)_2RuCl_2(PPh_3)] 2, which was further converted into the cationic diphosphine derivatives [(Cp~*Ir)_2(#mu#_3-S)_2RuCl_2RuCl(L)]Cl (L = dppe = Ph_2PCH_2CH_2PPh_2 3 or depe = Et_2PCH_2CH_2PEt_2 4). The reaction of cluster 3 with Me_2CuLi followed by anion metathesis with KPF_6 afforded the cationic methyl cluster [(Cp~*Ir)_2(#mu#-S)_rUe(dope)][PF_6] in good yield, while treatment of 3 with CHCl_2Li led to selective formation of [(Cp~*Ir){(#eta#~4-C_5Me_5CHCl_2)Ir}(#mu#_3-S)_2RuCl(dppe)] 6, in which one of the Cp~* ligands was alkylated by CHCl_2Li to form an #eta#~4-diene. Clusters 3 and 4 were also transformed into the dihydrido clusters [(Cp~*Ir)_2(#mu#_3-S)_2(#mu#-H)_2Ru(L)](L = dppe 7 or depe 8) by the reaction with NaBH_4. On the other hand, cluster 2 was converted into the carbonyl cluster [(Cp~*Ir)_2(#mu#_3-S)_2RuCl(CO)(PPh_3)]Cl 9, the isocyanide clusters [(Cp~*Ir)_(2-) (#mu#_3-S)_2RuCl(CNXy)(PPh_3)]Cl 10 (Xy = 2, 6-C_6H_3Me_2) and [(Cp~*Ir)_2(#mu#_3-S)_2Ru(CNXy)_2(PPh_3)][BPh_4]_2 11 and the co-ordinatively unsaturated thiolato clusters [(Cp~*Ir)_2(#mu#_3-S)Ru(SAr)_2] (Ar =2, 4, 6-C_6H_2Pr_3~i 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular structures of [(Cp~*Ir)_2(#mu#-S)_2 RuCl(depe)][BPh_4] 4', 5 centre dot CH_2Cl_2, 6, 7 and 12 centre dot 2C_6H_6 were established by X-ray diffraction studies.