Charge Effects on Oxygen Atom Transfer

The rhenium(V) complex [(HCpz3)ReOCl2]+ ([1]+), the tris(pyrazolyl)methane analogue of the known tris(pyrazolyl)borate complex (HBpz3)ReOCl2 (2), has been prepared. The two complexes are strikingly similar, as are the phosphine oxide adducts [(HCpz3)ReCl2(OPPh3)]Cl ([3]Cl) and (HBpz3)ReCl2(OPPh3) (4), which have been characterized by X-ray crystallography. Comparison of the bimolecular reduction of [1]BF4 and 2 by triarylphosphines reveals a pronounced charge effect, with the cationic species being reduced by PPh3 about 1000 times faster than its neutral analogue in CH2Cl2 at room temperature. Ligand substitution of the adducts [3]+ and 4 is dissociative, with the cationic complex dissociating phosphine oxide about 56 times more slowly than the neutral compound. The relative impact of charge on ground and transition states in atom transfer reactions is discussed.