Abstract
Synthesis and Reactions of Hydrido(oxime), Hydrido(oximato) and Alkenyl(oximato) Complexes of Ruthenium and OsmiumThe carbonyl(hydrido) complexes MHCl(CO)[PMe(tBu)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(tBu)2]2 (8–13) in high yields. Using MHCl(CO)(PiPr3)2 (6, 7) as starting materials, the complexes MHCl(CO)[N(OH)=CRR′](PiPr3)2 (14–16) are obtained. Reactions of 9 (M = Os; R = R′ = CH3) 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(tBu)2)2]2 (18: M = Os; 27: M = Ru) with Na[N(O) = CRR′].
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