摘要 : New mono- and dicarbonyl phosphane Re-I complexes [ReCl(L)(2)(CO)(PPh3)2] [L = 3,5-Me-2-Hpz (3), quin (4)} and [Re(L)(n)(CO)(2)(PPh3)(2)][BPh4](m) [L = pz/Hpz, n = 2, m 0 (2); L = 4,7-Ph-2-phen, n = 1, m = 1 (5); L = 2-Me-dipic, n... 展开 New mono- and dicarbonyl phosphane Re-I complexes [ReCl(L)(2)(CO)(PPh3)2] [L = 3,5-Me-2-Hpz (3), quin (4)} and [Re(L)(n)(CO)(2)(PPh3)(2)][BPh4](m) [L = pz/Hpz, n = 2, m 0 (2); L = 4,7-Ph-2-phen, n = 1, m = 1 (5); L = 2-Me-dipic, n = 1, m = 0 (6)) were prepared by reaction of the dinitrogen Re-I precursor [ReCl(N-2)(CO)(2)(PPh3)(2)] (1), in refluxing methanol or methanol/benzene mixture, with 3,5-dimethylpyrazole (3,5-Me-2-Hpz), quinoline (quin), pyrazole (Hpz), 4,7-diphenyl-1,10-phenanthroline (4,7-Ph2-phen) and dipicolinic acid (H(2)dipic), respectively, with esterification of the latter in 6 to afford the 2-methoxycarbonyl-6-pyridinecarboxylate (2-Me-dipic) moiety. Complexes 2-6 were characterized by IR spectroscopy, H-1-, P-31{H-1}- and C-13{H-1} NMR spectroscopy, FAB-MS, cyclic voltammetry, elemental analyses and single-crystal X-ray diffraction (for 2, 5 and 6) analyses which indicate mutually trans triphenylphosphane ligands. The redox behaviour of the obtained complexes in solution was studied, and the Lever electrochemical ligand parameter E-L was determined, for the first time, for 4,7-Ph-2-phen. Compounds 2-6 represent the first examples of mono- and dicarbonyl Re complexes bearing these types of ligands. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007. 收起