Synthesis, structure and redox behaviour of facial [ReIIIL(PPh3)Cl3] and its stereoretentive conversion to [ReIVL′(PPh3)Cl3] via metal promoted aldimine→amide oxidation (L = pyridine-2-aldimine; L′ = pyridine-2-carboxamide

被引:31
作者
Bhattacharyya, S [1 ]
Banerjee, S [1 ]
Dirghangi, BK [1 ]
Menon, M [1 ]
Chakravorty, A [1 ]
机构
[1] Indian Assoc Cultivat Sci, Dept Inorgan Chem, Calcutta 700032, W Bengal, India
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1999年 / 02期
关键词
D O I
10.1039/a806346j
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of mer-[(ReL)-L-III(OPPH3)Cl-3] 2 with PPh3 in benzene has afforded bluish violet fac-[(ReL)-L-III(PPh3)Cl-3] 1, where L is the Schiff base of pyridine-2-carbaldehyde and the substituted aniline p-XC6H4NH2 (X = H, Me, OMe or Cl). Geometrical preferences are rationalized in terms of the electronic nature of the ligands OPPh3 (sigma- and pi- donor), PPh3 (sigma-donor and pi-acceptor) and L (sigma-donor and pi-acceptor). The cyclic voltammetric E-1/2 values of 1 lie near 0.6 V (Re-IV-Re-III) and -0.6 V (Re-III-Re-II). Electrooxidation of 1 at 1.0 V vs. SCE in wet acetonitrile affords yellow fac-[(ReL)-L-IV'(PPh3)Cl-3] 3 which is also obtainable via oxidation by dilute nitric acid (L' is a monoanionic pyridine-2-carboxamide). Complex 3 displays Re-IV-Re-III and Re-V-Re-IV couples near -0.2 V and 1.4 V respectively reflecting superior stabilization of the rhenium(IV) state by the amide ligand. The X-ray structures of two representative complexes of type 1 and 3 have revealed the presence of severely distorted and facially configured RePN2Cl3 coordination spheres. The average Re-Cl distance is lower by 0.06 Angstrom in 3 due to contraction of the metal radius upon oxidation. The Re-P length is however larger by 0.1 Angstrom in 3 signifying a weakening of Re-P back-bonding.
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页码:155 / 159
页数:5
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