HOMOBINUCLEAR AND HETEROBINUCLEAR COMPLEXES CONTAINING THE ANION [RH(C5ME5)(PO(OME)2)2(PYRAZOLATE)]- AS LIGAND - CRYSTAL-STRUCTURE OF [(C5ME5)RH(MU-PO(OME)2)2(MU-C3H3N2)-RU(C6H6)]CLO4.CH2CL2
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Date
1992
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Abstract
The neutral rhodium(III) complex [Rh(C5Me5)I{PO(OMe)2}{P(OH)(OMe)2}] reacts with pyrazole-type ligands [HL = pyrazole (Hpz), 3-methylpyrazole, or 3,5-dimethylpyrazole] in the presence of AgClO4 yielding cationic complexes of the general formula [Rh(C5Me5){PO(OMe)2}{P(OH)(OMe)2}(HL)]ClO4. They react with Na2CO3 in aqueous solutions with formation of the neutral complexes [Rh(C5Me5){PO(OMe)2}2(HL)]. Addition of NaH in tetrahydrofuran to the cationic complexes or thallium acetylacetonate in MeOH to the neutral compounds affords the corresponding bimetallic derivatives [(C5Me5)Rh{PO(OMe)2}2LM] (M = Na or Tl). These complexes react with halide compounds such as [{M(ring)Cl2}2] [M(ring) = Rh(C5Me5), Ir(C5Me5), Ru(C6H6), Ru(C6H5Me), Ru(MeC6H4Pri-p) or Ru(C6Me6)], [MBr(CO)5], [(PtMe3I)4] or [{Rh(mu-Cl)(cod)}2] (cod = cycloocta-1,5-diene) to give cationic or neutral complexes of the type [(C5Me5)Rh{mu-PO(OMe)2}2(mu-L)M(ring)]ClO4 or [(C5Me5)Rh{PO(OMe)2}2(mu-L)MLn] [ML(n) = Re(CO)3, Mn(CO)3, PtMe3 or Rh(cod)]. The crystals structure of [(C5Me5)Rh{mu-PO(OMe)2}2(mu-pz)Ru(C6H6)]ClO4.CH2Cl2 has been determined by X-ray diffraction methods:monoclinic,space group P2(1)/c, a = 1.179(1), b = 17.039(1), c = 18.186(2) angstrom, beta = 94.85(1)-degrees and Z = 4. The complex cation consists of one rhodium and one ruthenium atom bridged by two phosphonate and one pyrazolate anion. An eta5-C5Me5 and an eta6-C6Me6 group complete the co-ordination spheres of the metals, which show no direct intermetallic interaction.