Inorganic Chemistry, Vol.34, No.6, 1304-1305, 1995
A Unique 3-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(OEt)(3)(Mu-Wos3)(CuCl)Cu)(2)(Mu-Cl)(2)) with a Linked Incomplete Cubane-Type Structure
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.