Yuri S. Varshavsky

31P-NMR and X-ray studies of new rhodium(I) β-ketoiminato complexes Rh(R1C(O)CHC(NH)R2)(CO)(PZ3) where PZ3=PPh3, PCy3, P(OPh)3 or P(NC4H4)3

Abstract The substitution of the CO ligand in rhodium(I) β-ketoiminato complexes Rh(R1{O,N}R2)(CO)2 ({O,N}=R1C(O)CHC(NH)R2; R1, R2=CF3, Me, CMe3 in several combinations) by phosphorus ligands PZ3 (PZ3=PCy3, PPh3, P(OPh)3, P(NC4H4)3) leads to Rh(R1{O,N}R2)(CO)(PZ3) complexes characterised by 31P{1H}-NMR and X-ray methods. The stronger σ-donor PZ3 ligands (PZ3=PCy3, PPh3) substitute almost exclusively the CO group trans to N, forming P-trans-to-N isomers. The complexes Rh(CF3{O,N}Me)(CO)(PCy3) (II), Rh(CF3{O,N}CMe3)(CO)(PCy3) (III), Rh(CF3{O,N}Me)(CO)(PPh3) (IV) and Rh(CF3{O,N}CMe)(CO)(PPh3) (V) are of a square-planar geometry with a slight tetrahedral distortion around the rhodium atom in II, III and V. The RhP(PCy3) bonds are slightly longer than the RhP(PPh3) bonds. The reaction of stoichiometric amounts of the less basic P(OPh)3 or P(NC4H4)3 ligands leads to the formation of both isomers of the Rh(R1{O,N}R2)(CO)(P(OPh)3) or Rh(R1{O,N}R2)(CO)(P(NC4H4)3) complex in comparable yields. The RhP(P(OPh)3) distance (2.195(2) A) in the isomer of Rh(CF3{O,N}CMe3)(CO)(P(OPh)3) with P(OPh)3 coordinated trans to N (VI) is ca. 0.04 A longer than in the isomer of that complex with P(OPh)3 coordinated trans to O (VII). The CO substitution in Rh(R1{O,N}R2)(CO)2 by PZ3 ligands (PPh3, PCy3, P(OPh)3) causes the shortening of the RhC(CO) bond by ca. 0.04 A compared to Rh(CF3{O,N}Me)(CO)2 (I), making difficult the coordination of another PZ3 ligand, especially one with stronger σ-donor properties. The more π-acceptor P(OPh)3 ligands form bis-phosphito complexes and Rh(CF3{O,N}CMe3){P(OPh)3}2 (VIII) exhibits inequivalence of the two P(OPh)3 ligands in solution (31P-NMR) as well as in solid form (X-ray).

Dirhodium(II) dicarboxylato complexes containing carbonyl and C-bonded methoxycarbonyl ligands

Abstract Oxidation of rhodium(I) carbonyl chloride, [Rh(CO) 2 Cl] 2 , with copper(II) acetate or isobutyrate in methanol solutions yields binuclear double carboxylato bridged rhodium(II) complexes with RhRh bonds, [Rh(μ-OOCRκO)(COOMeκC)(CO)(MeOH)] 2 , where R=CH 3 or i -C 3 H 7 . According to X-ray data, surrounding of each rhodium atom in these complexes is close to octahedral and consists of another rhodium atom, two oxygens of carboxylato ligands, terminal carbonyl group, C-bonded methoxycarbonyl ligand, and axial CH 3 OH. Methoxycarbonyl ligand is shown to originate from CO group of the parent [Rh(CO) 2 Cl] 2 and OCH 3 group of solvent. N- and P-donor ligands L ( p -CH 3 C 6 H 4 NH 2 , P(OPh) 3 , PPh 3 , PCy 3 ) readily replace the axial MeOH yielding [Rh(μ-OOCRκO)(COOMeκC)(CO)(L)] 2 . The X-ray data for the complex with R= i -C 3 H 7 , L=PPh 3 showed the same molecular outline as with L=MeOH. Electronic effects of axial ligands L on the spectral parameters of terminal carbonyl group are essentially the same as in the known series of rhodium(I) complexes (an increase of δ 13 C and a decrease of ν (CO) with strengthening of σ-donor and weakening of π-acceptor ability of L).