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(PR3)(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(PPr3i)(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 derivatives 7b and 7c yields the paramagnetic tetrahedral homonuclear cationic cluster Cp4Cr4S4+O3SCF3- (10) and the binuclear methylated Cp2Cr2(SCMe3)(2)(SMe)+O3SCF3- (11), respectively. The reaction of compound affords the antiferromagnetic heteronuclear cluster Cp2Cr2(SCMe3)S2PdCl(PPr3i) (12). The structure of the core of 12 is analogous to the structures 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), whereas the heteronuclear complex (CO)(6)Fe2S2Pd(PPr3i)(2) (16) was found only in trace amounts. The reasons for the difference in the reactivities of the rhenium and palladium derivatives toward compounds 1 and 5 are 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.