SYNTHESES, STRUCTURES AND PROPERTIES OF HYDROSULFIDO-BRIDGED DIIRIDIUM AND DIRHODIUM COMPLEXES, [CP-ASTERISK-MCL(MU(2)-SH)(2)MCP-ASTERISK-CL] AND [CP-ASTERISK-M(MU(2)-SH)(3)MCP-ASTERISK](-ASTERISK = ETA(5)-C5ME5)() (M = IR, RH, CP)

The reaction of [CpMCl(mu(2)-Cl)(2)MCp*Cl] (M = Ir, Rh; Cp* = eta(5)- C5Me5) with excess H2S gas for 5 min afforded the doubly bridged hydro sulfido complexes [CpMCl(mu(2)-SH)(2)MCp*Cl] (3: M = Ir, 4: M = Rh) w hich were further transformed into the triply bridged cationic hydrosu lfido complexes [CpM(mu(2)-SH)(3)MCp*]Cl(5 . Cl:M = Ir, 6 . Cl: M = R h) by continuous stirring under H2S. The molecular structures of 3, 4, 5 .[BPh4] and 6 . Cl . C6H6 were determined by X-ray analyses. The SH ligands in complexes 3 and 4 take anti configuration in the solid sta te, whilst these complexes exist as mixtures of the syn and anti isome rs in solution. Strong hydrogen bonds between the Cl anion and two of the SH ligands were found in 5 . Cl and 6 . Cl, and were maintained in CDCl3 solution. When complexes 3 and 4 were treated with NEt3 at room temperature, the cubane-type sulfide clusters [(CpM)(4)(mu(3)-S)(4)] (M=Ir, Rh) were produced in high yields. In the reaction of 3, an int ermediary complex, most probably [CpIr(mu(2)-S)(2)IrCp*], was detecte d by H-1 NMR. (C) 1998 Elsevier Science S.A.