Heterobinuclear IrRh, RuRh and RuIr Complexes with Pyrazolate Bridging Ligands: Reactivity towards Chelating Diphosphines; Crystal Structure of BPh4*0.5MeOH

Article abstract of DOI:10.1039/DT9910002811

Complexes of general formula 1-5 and <(MeC6H4Prⁱ-p)Ru(μ-pz)(μ-Cl)2Rh(cod)> 7 were prepared starting from mononuclear acetylacetonate and pyrazole or pyrazolate-containing moieties.Complexes 1-5 react with CO yielding derivatives 8-12.Complexes <(C5Me5)ClRh(μ-pz)2Rh(CO)2> 13 and <(MeC6H4Prⁱ-p)ClRu(μ-pz)2Ir(CO)2> 12 react with NaX to give <(C5Me5)XRh(μ-pz)2Rh(CO)2> (X = I; 14; or N3, 15) and <(MeC6H4Prⁱ-p)Ru(μ-pz)2IrX(CO)2> (X = Br, 16; or I, 17.The dicarbonyl compound 10 and <(MeC6H4Prⁱ-p)ClRu(μ-pz)2M'(CO)2> (M' = Rh, 11; or Ir, 12) react with diphosphines (L-L) or 1,2-bis(diphenylarsino)ethane (dpae) and NaBPh4 or AgBF4 affording cationic complexes >A 23-31 A = BPh4 or BF4 (not all possible combinations)>.In this reaction intermediates >A have been isolated in some cases.The crystal structure of one of these <(C5Me5)Ir(μ-pz)2(μ-CO)Ir(CO)(dppen)>BPh4*0.5MeOH 19 has been determined by X-ray diffraction methods.Crystals are monoclinic, space group P2₁/c, a = 15.996(2), b = 22.199(4), c = 18.874(3) Angstroem, β = 115.04(1) deg and Z = 4.The complex cation consists of two iridium atoms bridged by two pyrazolates and one ketonic carbonyl group.An η⁵-C5Me5 ligand, a chelate dppen and a terminal CO group complete the co-ordination spheres of the iridium atoms, which are separated by 3.440(5) Angstroem.

Full text of DOI:10.1039/DT9910002811

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