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Homo- and hetero-binuclear complexes containing the anion [Rh(C5Me5){PO(OMe)2}2(pyrazolate)]– as ligand. Crystal structure of [(C5Me5)Rh{µ-PO(OMe)2}2(µ-C3H3N2)-Ru(C6H6)]ClO4·CH2Cl2

AuthorsValderrama, Mauricio; Carmona, Daniel ; Lamata, M. Pilar ; Lahoz, Fernando J. ; Oñate, Enrique ; Oro, Luis A.
Issue Date1992
PublisherRoyal Society of Chemistry (UK)
CitationJournal of the Chemical Society 18: 2735-2741 (1992)
AbstractThe 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(μ-Cl)(cod)}2] (cod = cycloocta-1,5-diene) to give cationic or netural complexes of the type [(C5Me5)Rh{μ-PO(OMe)2} 2(μ-L)-M(ring)]ClO4 or [(C5Me5)Rh{PO(OMe)2}2(μ-L)ML n] [MLn = Re(CO)3, Mn(CO)3, PtMe3 or Rh(cod)]. The crystal structure of [(C5Me5)Rh{μ-PO(OMe)2} 2(μ-pz)Ru(C6H6)]ClO 4·CH2Cl2 has been determined by X-ray diffraction methods: monoclinic, space group P21/c, a = 11.179(1), b = 17.039(1), c = 18.186(2) Å, β = 94.85(1)° and Z = 4. The complex cation consists of one rhodium and one ruthenium atom bridged by two phosphonate and one pyrazolate anion. An η5-C5Me5 and an η6-C6Me6 group complete the co-ordination spheres of the metals, which show no direct intermetallic interaction.
Identifiersdoi: 10.1039/DT9920002735
issn: 0368-1769
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