Oxidorhenium(V) complexes of a family of bipyridine-like ligands including pyridyltriazines and pyrazinyltriazine: Oxygen-atom transfer, metal redox and correlations

摘要

The title ligands (general abbreviation L) are bipyridine (bpy), its dimethyl (mbpy) and diphenyl (pbpy) derivatives, phenanthroline (phen), 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine (ppyt) and its dimethyl (mpyt) and pyrazinyl (ppzt) analogues. The concerned oxido complexes are [ReOCl3(L)], [ReOBr3(ppyt)] and [ReOBr3(ppzt)]. The chloro and bromo complexes of ppyt and ppzt were prepared by reacting these ligands with [ReOX3(AsPh3)(2)] (X = Cl, Br). The X-ray structures of [ReOCl3(ppyt)] and [ReOCl3(ppzt)] reveal that the ReCl3 fragment is meridionally disposed and that the L ligand is N,N-coordinated such that the pyridine/pyrazine nitrogen lies trans to the oxido oxygen atom. The Re-O lengths [1.656(10)/1.625(9) angstrom] correspond to approximate triple bonding. The rate of oxygen-atom transfer from [ReOX3(L)] to triphenylphosphane in solution follows second-order kinetics and is associated with a large and negative entropy of activation (approx. -30 cal K-1 mol(-1)). The initial attack is believed to involve the phosphane lone pair and Re O pi(center dot-)orbitals. Electron withdrawal from the (ReO)-O-V moiety by varying X or L facilitates oxygen-atom transfer. Thus, the rates follow the orders Br < Cl; mbpy < bpy < phen < pbpy mpyt < ppyt < ppzt. The reduction potential of the quasi-reversible (ReO)-O-VI/(ReO)-O-V couple displays similar trends and the logarithmic rate constant of oxygen-atom transfer is found to correlate linearly with the reduction potential. (c) Wiley-VCH Verlag GmbH & Co. KGaA.