An unusual selective reduction of an oxime into an imine group in halogenomethyl rhodoximes
作者： Dirk Steinborn , Mario Rausch , Clemens Bruhn
DOI: 10.1016/S0022-328X(98)00534-8
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摘要: Abstract [Rh(dmgH) 2 (PPh 3 )] − ([Rh] , 1 ) {[Rh]=[Rh(dmgH) )]; (dmgH) =dimethylglyoxime}, obtained by reduction of [Rh]–Cl with NaBH 4 in methanolic KOH, reacts dihalogenomethanes CH X (X=Br, Cl) to give besides the known complexes [Rh]–CH 2a ; X=Cl, 2b [Rh(CH X){ONC(Me)–C(Me)NH}(dmgH)(PPh 3a 3b where one oxime unit is reduced an imine. Due strong alkaline medium (methanolic KOH) was found react partially, yielding OMe){ONC(Me)–C(Me)NH}(dmgH)(PPh ( 3c ). All three were characterized H-, 13 C-, 31 P-NMR spectroscopy. crystallizes triclinic space group P two molecules asymmetric unit. These are linked via N–H⋯O hydrogen bridges forming a dimer. The rhodium atoms display distorted octahedral coordination dmgH/ONC(Me)–C(Me)NH ligands equatorial plane and PPh Br axial positions.
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