14875-00-4Relevant articles and documents
Preparation and Reactivity of Iodomethyl Complexes of Rhodium(III); Crystal and Molecular Structure of Carbonylchloroiodo(iodomethyl)bis(triethylphosphine)rhodium(III)
Gash, Rosslyn C.,Cole-Hamilton, David J.,Whyman, Robin,Barnes, John C.,Simpson, Michael C.
, p. 1963 - 1970 (2007/10/02)
Diiodomethane oxidatively added to formed for R3=Me3, Et3 or Et2Ph but not for R3=EtPh2, Ph3, (C6H11)3 or (OMe)3; CH2Br2 gave a mixture of bromo- and chloromethyl complexes whilst CH2ICl gave two isomers of with I or Cl trans to CH2Cl.In polar solvents or on treatment with water or MeOH, underwent a halide-scrambling reaction to give several compounds containing CH2I or CH2Cl ligands which have been identified spectroscopically.The same scrambling occurs under high pressures of CO, although IR, NMR and model studies suggest the Rh-C(O)CH2X species are also formed by insertion of CO into the Rh-CH2X bond.Most of the acyl products are unstable to loss of ketene, but one may be stable -1>.The complex has been characterised crystallographically: triclinic, space group P, a=12.343(3), b=14.327(2), c=15.426(2) Angstroem, α=113.78(1), β=67.25(1), γ=90.20(1) deg, Z=4, R=0.0453.Each unit cell contains two pairs of molecules differing in the relative orientations of one PEt3 ligand.In both cases, Rh-C , C-I and Rh-C-I are similar to those reported for related compounds.Both molecules have mutually trans phosphines and CH2I trans to I.
Substitution of CO by picolines and amines in RhCl(CO)(PR3)2. Synthesis and crystal structure of cis-RhCl(3-pic)2
Trzeciak, A. M.,Ziolkowski, J. J.,Lis, T.
, p. 391 - 398 (2007/10/02)
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.
