16634-10-9Relevant academic research and scientific papers
Heterobimetallic complexes of rhenium and ruthenium containing methylaminobis(difluorophosphine)
Mague, Joel T.,Lin, Zhaiwei
, p. 3027 - 3037 (2008/10/08)
The syntheses of cpRuCl(η1-MeN(PF2)2)2 (1) and fac-ReBr(CO)3(η1-MeN(PF2)2) 2 (3) are described together with their use in the directed synthesis of heterobimetallic complexes. The monodentate MeN(PF2)2 ligands in 1 are cleaved on exposure to moisture or on chromatography on Florisil to give cpRu(P(O)F2)(PF2NHMe)2 (2). With Co2(CO)8 1 and 3 respectively yield cpRu(μ-MeN(PF2)2)2Co(CO)2 (4) and fac-Re(CO)3(μ-MeN(PF2)2) 2Co(CO)2 (5), while with IrCl(CO)(PPh3)2, cpRu(μ-MeN(PF2)2)2IrCl2(PPh 3) (6) and fac-Re(CO)3(μ-MeN-(PF2)2) 2IrClBr(PPh3) (7) are obtained. Complex 1 and [RhCl(CO)2]2 yield cpRu(μ-MeN(PF2)2)2-RhCl2 (8) which adds dimethylphenylphosphine to give cpRu(μ-MeN(PF2)2)2RhCl2(PMe 2Ph) (9) while with 3 the product is fac-Re(CO)3(μ-MeN(PF2)2)2RhClBr (10). A complex mixture of products is formed from 1 and Pt(L)(PPh3)2 (L = C2H4, C2Ph2) which has not been completely characterized, but fac-Re(CO)3(μ-MeN(PF2)2) 2PtBr(PPh3) (11), in which the platinum adopts a distorted square pyramidal coordination with a very long apical Pt-Br bond, is obtained from 3 and Pt(C2Ph2)(PPh3)2. The structures of 2, 5, 9, and 11 have been determined by X-ray crystallography. 2: monoclinic; P21/n; a = 10.487(2), b = 11.832(2), c = 11.910(2) A?; β = 90.50(1)°; Z = 4. 5: triclinic; P1; a = 9.794(1), b = 10.563(1), c = 9.624-(2) A?; α = 98.06(1), β = 101.29(1), γ = 81.796(9)°; Z = 2. 9: monoclinic; P21/c; a = 18.239-(3), b = 8.195(2), c = 18.078(2) A?, β = 102.36(1)°; Z = 4. 11: monoclinic; C2/m; a = 12.649(2), b = 14.908(1), c = 19.798(2) A?; β = 96.600(9)°; Z = 4.
Dinuclear Complexes of Rhodium and Iridium with Cyanide or Thiocyanate Bridges: Molecular Structure of
Deeming, Antony J.,Proud, Graeme P.,Dawes, Helen M.,Hursthouse, Michael B.
, p. 2475 - 2482 (2007/10/02)
Reactions of the rhodium or iridium complexes with give the homometallic cyano-bridged compounds (M = M' = Rh or Ir) and the corresponding heterometallic isomers which do not interconvert.The crystal structure of the complex revealed that the two IrCl2(PMe2Ph)3 groups are symmetry related because there is a disordered distribution of IrCNIr and IrNCIr orientations.Hence, though the structure is well refined (R = 0.035), the different structural influences of the C and N atoms in the bridge could not be defined.However, 13C, 15N, and 31P n. m. r. studies reveal that the trans influence of C is greater than that of the N atom.The corresponding homometallic compounds (ClO4> (M = Rh or Ir) were obtained but attempted synthesis of the mixed Rh/Ir compounds led to a mixture of all four possible homo- and hetero-metallic species.We conclude that the thiocyanato bridges can cleave to give both S- and N-bonded mononuclear species but N-bonded cyanide monomers are inaccessible.
Tertiary phosphine complexes of rhodium(I) and rhodium(III) chlorides
Intille
, p. 695 - 702 (2008/10/08)
The most complete series of tertiary phosphine complexes of rhodium yet reported has been prepared. Depending on the particular phosphine and the method of preparation, several different types of complexes may be formed. These include RhCl3(PR
