Substitution of CO by picolines and amines in RhCl(CO)(PR3)2. Synthesis and crystal structure of cis-RhCl(3-pic)2

Article abstract of DOI:10.1016/0022-328X(91)80251-E

The title complex, cis-RhCl(3-pic)2 (3-pic = 3-picoline), has been prepared with two other isostructural rhodium complexes, respectively with 4-picoline and CH2=CH-CH2NH2.The RhCl(3-pic)2 compond crystallizes in space group P<*> with a = 10.531(6), b = 12.025(9), c = 15.943(8) Angstroem, α = 83.01(5), β = 79.46(4), γ = 86.33(5) deg; Z = 2.The RhCl(amine)2 complexes were obtained in the reactions of 2, 2 (cod = cycloocta-1,5-diene) or RhCl(CO)2 with amines.CO substitution by amines in RhCl(CO)(PR3)2 complexes is limited by steric properties of amine and PR3 ligands. 3-Picoline substitutes CO only in complexes with PR3 ligands with cone angle Θ <*> 140 deg.The rate of CO substitution by 2-picoline is less than half that by 3-picoline.