Mononuclear, dinuclear nickel(II) and heterodinuclear Zn(II)Ni(II) complexes as models for the active site of phosphatase

Parimala, S.; Kandaswamy, M.

doi:10.1016/s1387-7003(03)00243-0

Cited by 18 publications

(6 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The phosphodiester can bind with the catalyst by one Zn⋯O coordination linkage (e.g. the mono-point-binding model 34,59 ) or two Zn⋯O coordination linkages to the bimetallic centers (e.g. the dual-pointbinding model 9,[57][58][59] or the OH-bridging model 9,60 ) or the two Zn⋯O coordination bonds to the same metal center (the mono-center-dual-binding model).…”

Section: B Coordination and Binding Modesmentioning

confidence: 99%

Mechanistic investigation of the cleavage of phosphodiester catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc complex: a DFT study

et al. 2014

View full text Add to dashboard Cite

Density functional theory (DFT) was utilized to investigate the hydrolysis reaction mechanisms of phosphodiester BNPP (BNPP = bis(4-nitrophenyl)phosphate) catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc(ii) complex. We examined the nature of the nucleophilic reagent and the active form of the catalyst. The coordination and binding models of the catalyst-substrate complex were explored and we investigated two catalyst configurations (a ridge configuration and a plane configuration), four basic catalyst-substrate binding models (a mono-point-binding model, a dual-point-binding model, an OH-bridging model and a mono-center-dual-binding model) and two alternate roles for the metal-coordinated hydroxide ion (whether it acts as a nucleophile or as a general base to facilitate the deprotonation of a solvent molecule). The one-point-binding mode was found to be preferred to construct a starting reactant. Nine plausible reaction mechanisms were proposed and investigated. Mechanism 1, a stepwise SN2-type addition-substitution reaction involving a para-position nucleophilic attack and the configuration inversion of the phosphate, was found to be the most favorable pathway. All of the proposed pathways are derived from alternate mechanisms such as a ping-pong mechanism and an AP mechanism. The ping-pong mechanism in combination with the role of the metal-coordinated hydroxide ion acting as a nucleophile was found to be more competitive than the other mechanisms examined. Results reported in this paper are consistent with, and can be utilized to systematically interpret, the experimental observations in the literature.

show abstract

Section: B Coordination and Binding Modesmentioning

confidence: 99%

Mechanistic investigation of the cleavage of phosphodiester catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc complex: a DFT study

et al. 2014

View full text Add to dashboard Cite

show abstract

“…[1][2][3][4] Mononuclear manganese centres have been found in the oxygen evolving center (OEC) of photosystem II (PS-II) 5 and in numerous enzymes, 6 including the superoxide dismutase, Mn-SOD, 7 and Mn-dioxygenase. 8 Dinuclear manganese centres, on the other hand, have been found in various metalloenzymes, 14 including catalase, 9-11 Mn-ribonucleotide reductase 12 and arginase.…”

Section: Introductionmentioning

confidence: 99%

Designer ligands. part 15. synthesis and characterisation of novel Mn(lI), Ni(II) and Zn(II) complexes of 1,10-phenanthroline-derived ligands.

Wellington¹,

Kaye²,

Watkins³

2010

Arkivoc

View full text Add to dashboard Cite

Series of manganese(II), nickel(II) and zinc(II) complexes have been prepared using 1,10-phenanthroline-derived ligands, and their coordination geometries have been assigned using infrared data. It is apparent that, depending on the ligand, the metal centres adopt octahedral, tetrahedral and distorted tetrahedral coordination geometries. The catecholase activity of the manganese(II) complexes has also been investigated.

show abstract

“…Several examples of enzyme models show a nuclearity dependence on their catalytic activity. Often, the mononuclear complexes show either decreased or no activity compared to their dinuclear counterparts. − The ability to convert between an inactive mononuclear and active dinuclear species may lead to catalysts that can be turned on or off as needed.…”

Section: Introductionmentioning

confidence: 99%

Anion-Controlled Nuclearity in Nickel Complexes with Potentially Dinucleating, Poly(oxime) Amine Ligands

et al. 2005

View full text Add to dashboard Cite

Two new ligands consisting of bis(oxime) amine units tethered by a bridge have been synthesized. Their nickel chloride and nickel nitrate complexes have also been synthesized and characterized by X-ray crystallography, FTIR, mass spectrometry, and elemental analysis. One of these ligands, L1 (N,N,N',N'-tetra(1-propan-2-onyl oxime)-diamino-m-xylene), is always dinucleating, while the other ligand, L2 (N,N,N',N'-tetra(1-propan-2-onyl-oxime)-1,3-diaminopropane), shows an unusual anion dependence on the nuclearity. When nickel chloride is used, the ligand acts in a dinucleating manner and coordinates two nickels; however, when nickel nitrate is used, the ligand acts in a monodentate fashion and coordinates only one nickel. Once the mononuclear complex is formed, it is not possible to add a second nickel if Ni(NO(3))(2) is used as the nickel source; it is possible, however, to add a second nickel if NiCl(2) is used as the nickel source. The dinuclear complex can be converted to the mononuclear one by either using silver nitrate to exchange the chloride anions for nitrates or by dissolving the complex in water. Ni(2)(L1)Cl(4)(DMF)(2).DMF: orthorhombic, P2(1)2(1)2(1), a = 12.2524(11) A, b = 16.6145(15) A, c = 20.1234(19) A, V = 4096.5(6) A(3), Z = 4. [Ni(2)(L2)Cl(4)(DMF)](2).2DMF: triclinic, P-1, a = 12.5347(5) A, b = 12.5403(5) A, c = 14.3504(6) A, alpha = 67.348(1) degrees , beta = 69.705(1) degrees , gamma = 81.549(1) degrees , V = 1952.25(14) A(3), Z = 1. Ni(L2).(NO(3))(2): monoclinic, P2(1)/n, a = 9.6738(3) A, b = 30.2229(9) A, c = 15.8238(5) A, beta = 97.995(1) degrees , V = 4581.4(2) A(3), Z = 8.

show abstract

Mononuclear, dinuclear nickel(II) and heterodinuclear Zn(II)Ni(II) complexes as models for the active site of phosphatase

Cited by 18 publications

References 15 publications

Mechanistic investigation of the cleavage of phosphodiester catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc complex: a DFT study

Mechanistic investigation of the cleavage of phosphodiester catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc complex: a DFT study

Designer ligands. part 15. synthesis and characterisation of novel Mn(lI), Ni(II) and Zn(II) complexes of 1,10-phenanthroline-derived ligands.

Anion-Controlled Nuclearity in Nickel Complexes with Potentially Dinucleating, Poly(oxime) Amine Ligands

Contact Info

Product

Resources

About