Ultrafast pump-probe spectroscopy (lambda(pump) = 420 nm) was applied to study the photoaquation of PtBr62- complex. The excitation to d-d excited T-1(1g) state was followed by the formation of an intermediate absorption decaying with characteristic times of 370 fs, 2.2 and 15.2 ps. Two shorter times were attributed to the formation of the lower excited state (T-3(1g)) and its vibrational cooling accompanied by solvent relaxation. The longest time was interpreted as T-3(1g), transition to the hot ground state ((1)A(1g)) and the dissociation product (PtBr5(H2O)(-) complex). The scheme is consistent with the independence of the photoaquation quantum yield on the excitation wavelength. (C) 2007 Elsevier B.V. All rights reserved.