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

The hydrogensulfido-bridged diiridium complex [ClCp*Ir(mu-SH)(2)IrCp*Cl] re acted with [RuH2(PPh3)(4)] to give a mixed-metal trinuclear cluster with an Ir2Ru(mu(3)-S)(2) core [(Cp*Ir)(2)(mu(3)-S)(2)RuCl2(PPh3)] 2, which was fu rther converted into the cationic diphosphine derivatives [(Cp*Ir)(2)(mu(3) -S)(2)RuCl(L)]Cl (L=dppe=Ph2PCH2CH2PPh2 3 or depe=Et2PCH2CH2PEt2 4). The re action of cluster 3 with Me2CuLi followed by anion metathesis with KPF6 aff orded the cationic methyl cluster [(Cp*Ir)(2)(mu(3)-S)(2)RuMe(dppe)][PF6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formatio n of [(Cp*Ir){(eta(4)-C5Me5CHCl2)Ir}(mu(3)-S)(2)RuCl(dppe)] 6, in which one of the Cp* ligands was alkylated by CHCl2Li to form an eta(4)-diene. Clust ers 3 and 4 were also transformed into the dihydrido clusters [(Cp*Ir)(2)(m u(3)-S)(2)(mu-H)(2)Ru(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*I r)(2)(mu(3)-S)(2)RuCl(CO)(PPh3)]Cl 9, the isocyanide clusters [(Cp*Ir)(2)(m u(3)-S)(2)RuCl(CNXy)(PPh3)]Cl 10 (Xy=2,6-C6H3Me2) and [(Cp*Ir)(2)(mu(3)- S) (2)Ru(CNXy)(2)(PPh3)][BPh4](2) 11 and the co-ordinatively unsaturated thiol ato clusters [(Cp*Ir)(2)(mu(3)-S)(2)Ru(SAr)(2)] (Ar=2,4,6-C6H2Pr3i 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular stru ctures of [(Cp*Ir)(2)(mu(3)-S)(2)RuCl(depe)][BPh4] 4', 5 . CH2Cl2, 6, 7 and 12 . 2C(6)H(6) were established by X-ray diffraction studies.