HETEROMETALLIC CLUSTER COMPLEXES OF THE TYPES RE2(MU-PR2)(CO)8(HGY) AND REMO(MU-PR2)(ETA(5)-C5H5)(CO)6(HGY) (R=PH, CY, Y=CL, W(ETA(5)-C5H5)(CO)3)

Dinuclear complexes Re2(mu-H)(mu-PR2)(CO)8 and ReMo(mu-H)(mu-PR2)(eta5-C5H5)(CO)6 (IR = phenyl, cyclohexyl) were deprotonated and reacted as anions with HgCl2 to compounds of the both types Re2(mu-PR2)(CO)8(HgCl) and ReMo(mu-PR2)(eta5-C5H5)(CO)6(HgCl). The heterometallic three-membered cluster complexes correspond to an isolobal exchange of a proton against a cationic HgCl+ group. For one of the products ReMo(mu-PCy2)(eta5-C5H5)(CO)6(HgCl) has been shown its conversion with NaW(eta5-C5H5)(CO), to ReMo(mu-PCy2)(eta5-C5H5)(HgW(eta5-C5H5)(CO)3) under substitution of the chloro ligand, par example. The newly prepared compounds were characterized by means of IR, UV/VIS and P-31 NMR data. A complete determination of the molecular structure by single crystal analyses was done in the case Of Re2(mu-PCy2)-(CO)8(HgCl) and of ReMo(mu-PCy2)(eta5-C5H5)(CO)6(HgCl) which both are dimer because of the presence of an asymmetric dichloro bridge, and of ReMo(mu-PCy2)(eta5-C5H5)(CO)6(HgW(eta5-C5H5)(CO)3). The structural study illustrates through comparison the influence of various metal types on an interaction between centric and edge-bridged frontier orbitals in three-membered metal rings.