AI Article Synopsis
- Two dinuclear zinc(II) complexes, [Zn(2)(bpmp)(mu-OH)](ClO(4))(2) and [Zn(2)(bpmp)(H(2)O)(2)](ClO(4))(3), were synthesized and characterized, showing changes in metal coordination with pH.
- The study involved the transesterification reaction of a phosphate in the presence of these complexes, revealing that complex 2 was not reactive, while complex 1 significantly enhanced the reaction rate.
- Mechanistic investigations combining kinetic studies, various spectroscopic analyses, and computational methods revealed two different mechanisms that depend on the solvent, with an unusual bridging phosphate intermediate identified in DMSO.
Article Abstract
Dinuclear zinc(II) complexes [Zn(2)(bpmp)(mu-OH)](ClO(4))(2) (1) and [Zn(2)(bpmp)(H(2)O)(2)](ClO(4))(3) (2) (H-BPMP=2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol) have been synthesized, structurally characterized, and pH-driven changes in metal coordination observed. The transesterification reaction of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) in the presence of the two complexes was studied both in a water/DMSO (70:30) mixture and in DMSO. Complex 2 was not reactive whereas for 1 considerable rate enhancement of the spontaneous hydrolysis reaction was observed. A detailed mechanistic investigation by kinetic studies, spectroscopic measurements ((1)H, (31)P NMR spectroscopy), and ESI-MS analysis in conjunction with ab initio calculations was performed on 1. Based on these results, two medium-dependent mechanisms are presented and an unusual bridging phosphate intermediate is proposed for the process in DMSO.
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| http://dx.doi.org/10.1002/chem.200700104 | DOI Listing |
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