A UNIQUE THREE-STEP CYCLIC REACTION SEQUENCE OF HETEROTRIMETALLIC SULFIDE CLUSTERS - STRUCTURES AND PROPERTIES OF [(CP-ASTERISK-RHP(OET)(3)(MU-WS4)(CUCL)CU)(2)(MU-CL)(2)] (CP-ASTERISK=ETA(5)-C(5)ME(5)) WITH A BRANCHED STRUCTURE AND [(CP-ASTERISK-RHP(

摘要

The trinuclear cluster [Cp(*)RhP(OEt)(3)(mu-WS4)(CuCl)] (1) shows a unique three-step cyclic reaction sequence with significant structural changes. The cyclic reaction involves a regiospecific CuCl addition of 1 to form an octanuclear branched cluster, [Cp(*)RhP(OE)(3)(mu-WS4)(CuCl)Cu}(2)(mu-Cl)(2)] (2), substitution of one bridging S atom in the WS4 group in 2 by an O atom from H2O in dichloromethane to produce 3 linked incomplete cubane-type octanuclear cluster (Cp(*)RhP(OEt)(3)(mu-WOS3)(CuCl)Cu}(2)(mu-Cl)(2)] (3), and recovery of 1 from 3 based on a specific reactivity of the CuCl group(s) in 1 and 3 toward H2S. [References: 19]