112947-39-4Relevant articles and documents
Cationic complexes of rhodium(I) and iridium(I) with methyl- and phenylbis(dimethoxyphosphino)amine
Mague, Joel T.,Lloyd, Charles L.
, p. 983 - 993 (2008/10/08)
The ligand PhN(P(OMe)2)2 (L2) reacts with [Rh(COD)(acetone)x]ClO4 to form [Rh(COD)(L2)]ClO4, [Rh(L2)2]ClO4, and [Rh2(L2)4(μ-L2)](ClO 4)2 depending on the metal/ligand ratio used. By contrast MeN(P(OMe)2)2 (L2′) only forms [Rh2(L2′)2(μ-L 2′)2]2+ which was isolated as PF6-, BPh4-, ClO4-, and F3CSO3- salts. Other rhodium complexes of the latter ligand that were synthesized include [Rh(L2′)(DPPE)]ClO4, [Rh(L)(L2′)(DPPE)]ClO4 (L = CO, P(OMe)3), and [Rh2(L2′)2(μ-L 2″)2](ClO4)2 (L2″ = 2,5-bis(diphenylphosphino)furan). The iridium analogue of the latter was also prepared as were several iridium complexes of MeN(P(OMe)2)2 including [Ir(L2′)(PPh3)2]ClO4, [Ir(L2′)2(PPh3)]ClO4, [Ir(CO)(L2′)(PPh3)2]ClO4, [Ir(L2′)3]ClO4, and [Ir(L2′)(BDPPF)]ClO4. The last appears to form five-coordinate adducts with O2 and dimethyl acetylenedicarboxylate. With the exception of these last two, all the five-coordinate complexes prepared are proposed to adopt fluxional trigonal-bipyramidal structures. [Ir(CO)(L2′)(PPh3)2]ClO4 crystallizes in the monoclinic system with space group P21/c, a = 16.067 (2) A?2, b = 14.421 (2) A?, c = 1.9574 (4) A?, β = 102.49 (1)°, and Z = 4. Full-matrix least-squares refinement of 341 variables using 5462 data (I > 3σ(I)) led to final values of R and Rw of 0.037 and 0.048, respectively. The perchlorate ion is partially disordered. The complex adopts a distorted trigonal-bipyramidal structure with an equatorial carbonyl ligand. [Rh2(L2′)4](F3CSO 3)2 crystallizes in the monoclinic system with space group P21/c, a = 22.676 (4) A?, b = 19.079 (4) A?, c = 12.236 (7) A?, β = 97.12 (3)°, and Z = 4. Full-matrix least-squares refinement of 523 variables using 6097 data (I > 3σ(I)) led to final values of R and Rw of 0.055 and 0.083, respectively. One anion is severely disordered. The dimer cation contains two distorted square-planar rhodium atoms bridged by two MeN(P(OMe)2)2 ligands situated cis to one another. The coordination sphere of each metal is completed by a second ligand which chelates resulting in a basket-shaped species.
