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The rhodium(III) trisacetonitrile complexes: a re-investigation of the synthesis of fac- and mer- [RhCl3(CH3CN)3], their characterization by 2D NMR spectroscopy and the X-ray crystal structure of mer-[RhCl3(CH3CN)3] · CH3CN

1995; Elsevier BV; Volume: 240; Issue: 1-2 Linguagem: Inglês

10.1016/0020-1693(95)04585-6

1873-3255

Oliver Renn, Heinz Rüegger, Luigi M. Venanzi, J. Gallus, Völker Gramlich, Arianna Martelletti,

Lanthanide and Transition Metal Complexes

It is shown that the reaction of RhCl3·3H2O with acetonitrile normally produces mixtures of mer- and fac-[RhCl3(CH3CN)3] (1a and 1b, respectively). The IR and 1H NMR spectra of these isomers were re-investigated. Their two-dimensional (103Rh,1H) NMR spectra were also recorded. Equilibrium and exchange studies of 1a and 1b in CD3C were performed. It was found that in 1a the exchange rate of the nitrile molecule trans to Cl is much faster than those of mutually trans nitriles. Also the nitrile molecules in 1b underwent fast exchange in CD3CN; however, their rate was slightly faster than that of the more labile CH3CN in 1a. The X-ray crystal structure of mer-[RhCl3(CH3CN)3]·CH3CN (1c) was determined. Crystal data: triclinic space group P1, a = 12.200(10), b = 12.227(10), c = 12.270(11) Å, α = 115.95(7), β = 101.52(7), γ = 102.93(6)°, V = 1509(2) Å]3, Z = 4.