Mass spectrometric and spectroscopic studies on hydrolysis of phosphoesters by bis(μ-acetato)-μ-phenolato dinuclear metal(II) complexes (metal = Mn, Co, Ni, and Zn)

Reiko Jikido, Hitomi Shiraishi, Kanako Matsufuji, Masaaki Ohba, Hideki Furutachi, Masatatsu Suzuki, Okawa Hisashi

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Dinuclear metal(II) complexes of 2,6-bis{N-[(2-dimethylamino)ethyl] iminomethyl}-4-methylphenol (HL), [Mn 2(L)(AcO) 2(NCS)] (1), [Co 2(L)(AcO) 2]BPh 4 (2), [Ni 2(L)(AcO) 2(MeOH)]BPh 4 (3), and [Zn 2(L)(AcO) 2]BPh 2 (4), have been examined as regards their hydrolytic activity toward tris(p-nitrophenyl) phosphate (TNP) and hydrogen bis(p-nitrophenyl) phosphate (HBNP) by means of mass spectrometric methods as well as UV-visible spectroscopic methods. All the complexes hydrolyze TNP to BNP - in the relative activity of 4 > 2 > 1 ≫ 3. It is found that one AcO - group of [M 2(L)(AcO) 2] + is replaced with BNP -, arising from the hydrolysis of TNP, affording [M 2(L)(AcO)(bnp)] + in an equilibrium with [M 2(L)(AcO) 2] +: [M 2 (L)(AcO) 2] + + BNP - ⇄ [M 2(L)(AcO)(bnp)] + + AcO -. In the reaction of HBNP with 1-4, [M 2(L)(AcO)(bnp)] + is produced in the equilibrium with [M 2(L)(AcO) 2] +, and the bound BNP - is slowly hydrolyzed in the case of M = Mn and Co. The bound BNP - of [Ni 2(L)(AcO)(bnp)] + is barely hydrolyzed and the bound BNP - of [Zn 2(L)(AcO)(bnp)] + is practically not hydrolyzed. The relevance of the complexes to phosphotriesterase and phosphodiesterase is discussed.

Original languageEnglish
Pages (from-to)1795-1803
Number of pages9
JournalBulletin of the Chemical Society of Japan
Issue number10
Publication statusPublished - Dec 1 2005


All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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