Crystal structure, solution properties and hydrolytic activity of an alkoxo-bridged dinuclear copper(II) complex, as a ribonuclease model

摘要

Crystal structures, solution properties and ribonuclease activity of copper() complexes of a binucleating, bis-pyridyl ligand (N,N'-bis(2-pyridylmethyl)-1,3-diaminopropan-2-ol, L) have been investigated. The single-crystal X-ray structure of the mononuclear complex [CuL(ClO4)(2)] (1) shows distorted octahedral geometry around the metal ion, with the four nitrogens of the ligand in the equatorial plane of copper(II). A mu-alkoxo-bridged dinuclear complex is formed in the presence of a two-fold metal excess. Despite the symmetrical ligand, the two metal ions in [Cu-2 (LH-1)( DPP)(ClO4)(CH3OH)]ClO4 (2, DPP = diphenyl phosphate) have distinct, distorted octahedral (Cul) and square pyramidal (Cu2) geometry. Beside the alkoxo-oxygen, the phosphate group of DPP also bridges the two metal centers in 2 in a mu-1,3-bridging mode. The complexes formed in aqueous solution are likely to have analogous structures to 1 and 2. The dinuclear [Cu-2(LH-1)( OH)] complex efficiently promotes the hydrolysis/transesterification of both activated (2-hydroxypropyl p-nitrophenyl phosphate, hpnp) and non-activated, biological phosphodiesters (uridine-2',3'-cyclic-monophosphate, cUMP and uridylyl-(3',5')-uridine, UpU). For example, a 2 mM solution of the dinuclear complex provides 5 orders of magnitude acceleration in the hydrolysis of cUMP. The proposed mechanisms include double Lewis-acid activation with intramolecular general base catalysis. [References: 37]