TY - JOUR
T1 - 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)
AU - Jikido, Reiko
AU - Shiraishi, Hitomi
AU - Matsufuji, Kanako
AU - Ohba, Masaaki
AU - Furutachi, Hideki
AU - Suzuki, Masatatsu
AU - Hisashi, Okawa
PY - 2005/12/1
Y1 - 2005/12/1
N2 - 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.
AB - 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.
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U2 - 10.1246/bcsj.78.1795
DO - 10.1246/bcsj.78.1795
M3 - Article
AN - SCOPUS:33750503422
SN - 0009-2673
VL - 78
SP - 1795
EP - 1803
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
IS - 10
ER -