Three Ni(II) complexes of cresol-based Schiffbase ligands, namely [Ni 2(L 1)(NCS) 3(H 2O) 2], (1) [Ni 2(L 2)- (CH 3COO)(NCS) 2(H 2O)] (2) and [Ni 2(L 3)(NCS) 3] (3), (where L 1 = 2,6-bis(N-ethylpyrrolidineiminomethyl)-4-methylphenolato, L 2 = 2,6-bis(N-ethylpiperidineiminomethyl)-4-methylphenolato and L 3 = 2,6-bis{N-ethyl-N-(3-hydroxypropyl iminomethyl)}-4- methylphenolato), have been synthesized and structurally characterized by X-ray single-crystal diffraction in addition to routine physicochemical techniques. Density functional theory calculations have been performed to understand the nature of the electronic spectra of the complexes. Complexes 1-3 when reacted with 4-nitrophenyl phosphate in 50:50 acetonitrile-water medium promote the cleavage of the O-P bond to form p-nitrophenol and smoothly convert 3,5-ditert- butylcatechol (3,5-DTBC) to 3,5-di-tert-butylquinone (3,5-DTBQ) either in MeOH or in MeCN medium. Phosphatase- and catecholase-like activities were monitored by UV-vis spectrophotometry and the Michaelis-Menten equation was applied to rationalize all the kinetic parameters. Upon treatment with urea, complexes 1 and 2 give rise to [Ni 2(L 1)(NCS) 2(NCO)(H 2O) 2] (1') and [Ni 2(L 2)- (CH 3COO)(NCO)(NCS)(H 2O)] (2') derivatives, respectively, whereas 3 remains unaltered under same reaction conditions. © Springer Science+Business Media B.V. 2011.