Synthese und Reaktionen von Hydrido(oxim)‐, Hydrido(oximato)‐ und Alkenyl(oximato)‐Komplexen des Rutheniums und Osmiums

Synthesis and Reactions of Hydrido(oxime), Hydrido(oximato) and Alkenyl(oximato) Complexes of Ruthenium and Osmium The carbonyl(hydrido) complexes MHCl(CO)[PMe( t Bu) 2 ] 2 ( 4 : M = Ru; 5 : M = Os) react with aldoximes and ketoximes to give the octahedral hydrido(oxime)ruthenium and ‐osmium compounds MHCl(CO)[N(OH)=CRR′](PMe( t Bu) 2 ] 2 ( 8–13 ) in high yields. Using MHCl(CO)(P i Pr 3 ) 2 ( 6, 7 ) as starting materials, the complexes MHCl(CO)[N(OH)=CRR′](P i Pr 3 ) 2 ( 14–16 ) are obtained. Reactions of 9 (M = Os; R = R′ = CH 3 ) illustrate that the oxime ligand in the hydrido(oxime) compounds is easily displaced by Lewis bases. Either from 4, 5 and Na[N(O) = CRR′] in methanol or from 8–13 and NaH in THF the hydrido(oximato) complexes 20–25 in which the oximato ligand is coordinated via N and O, are formed almost quantitatively. CO opens the three‐membered ring by cleavage of the M‐N bond. Analogously, the alkenyl(oximato) compounds 28–30 are obtained from M[( E )–CH = CHPh]Cl(CO)[PMe( t Bu) 2 ) 2 ] 2 ( 18 : M = Os; 27 : M = Ru) with Na[N(O) = CRR′].