FORMATION OF ANTIFERROMAGNETIC THIOLATE-BRIDGED AND SULFIDE-BRIDGED COMPLEXES .5. INTERACTIONS OF PHOSPHINEHALIDE COMPLEXES OF RE-I AND PD-II WITH ANTIFERROMAGNETIC CP2CR2(SCME3)(2)S AND DIAMAGNETIC FE3S2(CO)(9) COMPOUNDS

Reactions of Cp2Cr2(SCMe3)(2)S (1) with rhenium complexes (CO)(NO)Re(P R3)(2)X-2 [R = Et, X = Cl (7a); R = Et, X = O3SCF3 (7b); R = OMe, X = O3SCF3 (7c)] containing strongly bound phosphine ligands and with Pd(P Pr3i)(2)Cl-2 (8) containing bulky P donors were studied. The reaction between compounds 1 and 7a does not occur in various solvents within a temperature range of 22-80 degrees C. Interaction of 1 with triflat d erivatives 7b and 7c yields the paramagnetic tetrahedral homonuclear c ationic cluster Cp4Cr4S4+O3SCF3- (10) and the binuclear methylated Cp2 Cr2(SCMe3)(2)(SMe)+O3SCF3- (11), respectively. The reaction of compoun d affords the antiferromagnetic heteronuclear cluster Cp2Cr2(SCMe3)S2P dCl(PPr3i) (12). The structure of the core of 12 is analogous to the s tructures of the rhodium-containing complexes Cp2Cr2(mu-SCMe3)(mu(3)-S )(2)RhL2. Although compound 8 reacts with Fe3S2(CO)(9) (5), the major products are the homometallic trinuclear clusters Fe3S2(CO)(8)(PPr3i) (14) (as a mixture of isomers) and Fe3S2(CO)(7)(PPr3i)(2) (15), wherea s the heteronuclear complex (CO)(6)Fe2S2Pd(PPr3i)(2) (16) was found on ly in trace amounts. The reasons for the difference in the reactivitie s of the rhenium and palladium derivatives toward compounds 1 and 5 ar e discussed. The structures of complexes 10 (two crystal modifications ), 11, 12, 15, and 16 were established by X-ray structural analysis of the single crystals.