Aren- und cyclopentadienyl-halbsandwichkomplexe des rutheniums mit oximaten, carboxylaten, iminen und azavinylidenen als liganden

Abstract The reaction of [C 6 H 6 Ru(P i Pr 3 )Cl 2 ] ( 1 ) with NaONCRR′ in the presence of KPF 6 leads to the formation of the oximatoruthenium(II) complexes [C 6 H 6 Ru(η 2 -ONCRR′)(P i Pr 3 )]PF 6 ( 2 – 5 ) in 70–90% yield. Compound 5 (R  Me, R′  t Bu) reacts with HNCPh 2 via ligand exchange to give [C 6 H 6 Ru(NCPh 2 )(P i Pr 3 )]PF 6 ( 8 ). The azavinylidene complex 8 has also been prepared from the acetatoruthenium derivative [C 6 H 6 Ru(η 2 -O 2 CCH 3 )(P i Pr 3 )]PF 6 ( 6 ), which can be obtained either from 1 , CH 3 CO 2 Na and KPF 6 or from treatment of 5 with an excess of CH 3 CO 2 H. The synthesis of the hexamethylbenzeneruthenium compounds [C 6 Me 6 Ru(NCR′ 2 )PR 3 )]PF 6 ( 12 – 15 ) is achieved by the reaction of the hydrido(chloro)metal complexes [C 6 Me 6 RuH(PR 3 )Cl] ( 10 , 11 ) with oximes HONCR′ 2 and AgPF 6 . Nucleophilic addition of H − and CH 3 − to the NC carbon atom of [C 6 Me 6 Ru(NCPh 2 )(PMe 3 )] + affords the uncharged imitido compounds [C 6 Me 6 Ru(NCXPh 2 ) (PMe 3 )] ( 16 , 17 ). The cyclopentadienylruthenium complex [C 5 H 5 Ru(NCPh 2 )(PPh 3 )] ( 23 ) is prepared from either one of the imino derivatives [C 5 H 5 Ru(NHCPh 2 )(PPh 3 ) 2 ]BF 4 ·0.5CH 2 Cl 2 ( 22 ) or [C 5 H 5 Ru(NHCPh 2 )(PPh 3 )(O 2 CCH 3 )] ( 25 ) on treatment with NaR (R  H, C 5 H 5 ). Compound 25 reacts in toluene at room temperature by elimination of CH 3 CO 2 H to give the five-membered metallaheterocycle [C 5 H 5 Ru{NHC (Ph)C 6 H 4 }(PPh 3 )] ( 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 C 6 H 6 (P i Pr 3 )Ru and t Bu units at the NC double bond.