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• 4358-50-3 N,N-dimethyl-2-(diphenylphosphino)aniline 
• 53432-25-0 methyltetrakis(trimethylphosphane)cobalt(I) 

Relevant academic research and scientific papers

Fluxional and rigid (trimethylphosphane)cobalt complexes containing chelating (2-diphenylphosphanyl)anilido ligands

2-(Diphenylphosphanyl)anilines (P/NHR) eliminate methane upon reaction with [CoMe(PMe3])4] forming the complexes [Co(η2-P/NR)(PMe3)3] (1: R = H; 2: R = Me) and [Co(η2- P/NR)(PMe3)2] (3: R = Me). Reaction with HCl gives [CoCl(η1-P/NHR)(PMe3)2] (4: R = H; 5: R = Me) and reaction with CO or olefin gives [Co(η2-P/NR)(CO)(PMe3)2] (6: R = H; 7: R = Me) and [Co(η2-P/NR)(olefin)(PMe3)2] (8: R = H, olefin = C2H4; 9: R = Me, olefin = C2H4; 10: R = Me, olefin = C3H6), respectively. No catalytic transformation of the olefins was observed. Oxidation by iodomethane yields a cobalt(II) compound [CoI(ν2-P/NR)(PMe3)2] (11: R = Me). By treating 2 -(diphenylphosphanyl)aniline with [CoMe2(PMe3)3] a methylcobalt(II) complex [CoMe(η2-P/NR)(PMe3)2] (12: R = H) is obtained, while an excess of the aniline produces [Co(η2-P/NR)2] (13: R = H; 14: R = Me) or [Co(η2-P/NR)2(PMe3)] (15: R = H; 16: R = Me). The methylcobalt(III) complexes mer-trans-[CoIMe2(η2-P/NR) (PMe3)2] were obtained from LiP/NR and [CoClMe2(PMe3)3]. Dynamic 31P NMR spectra and the structures of complexes 3, 6, 12, and 13 are discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Regiospecific cyclometalation of diphenyl(2-substituted phenyl)phosphane with methyltetrakis(trimethylphosphane)cobalt(I)

The pre-chelate molecules 2-(diphenylphosphanyl)-N,N-dimethylaniline, [2-(diphenylphosphanyl)benzyl]dimethylamine, 1-(diphenylphosphanyl)-2-ethylbenzene, 1-(diphenylphosphanyl)-2-isopropylbenzene, and 2-(diphenylphosphanyl)benzonitrile, in a reaction with [CoMe(PMe3)4], eliminate methane to afford the selectively 6-ortho-metalated complexes 1-5 that contain four-membered metallacycles. The molecular structure of 3 shows a tbp-coordinated cobalt atom, with axial C and PMe3 donor groups. Metalation in the aliphatic side-chain occurs with 2-(diphenylphosphanyl)toluene, giving complex 6 that contains a five-membered metallacycle. Benzyldiphenylphosphane is selectively orthometalated in the benzyl group, affording 7. As shown by the molecular structures, complex 7 is a true ligand isomer of 6. Substitution of a trimethylphosphane group in compounds 4 and 6 by ethene gives the pentacoordinate complexes 8 and 9, respectively. The ethene ligand is π-coordinated in the equatorial plane of a trigonal bipyramid. Under 1 bar of CO, complex 6 forms monocarbonyl complex 10. Carbonylation of complexes 3 and 4 proceeds by insertion of CO into the Co-C bond under ring expansion, affording the aroylcobalt complexes 11 and 12, respectively. Complex 6 reacts with iodomethane in an oxidative substitution reaction yielding a structurally characterized octahedral complex mer-13, which eliminates a methyl group in THF at 20 °C to form a pentacoordinate cobalt(II) complex 14. Complex 3 oxidatively adds iodomethane in a stereoselective cis addition to give the cobalt(III) complex mer-15, which retains its four-membered metallacycle and the CoCH3 group. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.