Aren- und Cyclopentadienyl-Halbsandwichkomplexe des Rutheniums mit Oximaten, Carboxylaten, Iminen und Azavinylidenen als Liganden

Article abstract of DOI:10.1016/0022-328X(93)83372-3

The reaction of iPr3)Cl2> (1) with NaON=CRR' in the presence of KPF6 leads to the formation of the oximatoruthenium(II) complexes 2-ON=CRR')(PⁱPr3)>PF6 (2-5) in 70-90percent yield.Compound 5 (R=Me, R'=t-Bu) reacts with HN=CPh2 via ligand exchange to give iPr3)>PF6 (8).The azavinylidene complex 8 has also been prepared from the acetatoruthenium derivative 2-O2CCH3)(PⁱPr3)>PF6 (6), which can be obtained either from 1, CH3CO2Na and KPF6 or from treatment of 5 with an excess of CH3CO2H.The synthesis of the hexamethylbenzeneruthenium compounds PF6 (12-15) is achieved by the reaction of the hydrido(chloro)metal complexes (10, 11) with oximes HON=CR'2 and AgPF6.Nucleophilic addition of H^- and CH^-3 to the N=C carbon atom of ⁺ affords the uncharged imido compounds (16, 17).The cyclopentadienylruthenium complex (23) is prepared from either one of the imino derivatives BF4*0.5CH2Cl2 (22) or (25) on treatment with NaR (R=H, C5H5).Compound 25 reacts in toluene at room temperature by elimination of CH3CO2H to give the five-membered metallaheterocycle (26) which is an isomer of 23.The X-ray structural analysis of 5 reveals the presence of a O,N-bound oximato ligand and a cis position of the C6H6(PⁱPr3)Ru and t-Bu units at the N=C double bond.