Structure and synthesis of isomers of novel binuclear cobalt(III)-phenyl phosphate complexes

Jones, David R.; Lindoy, Leonard F.; Sargeson, Alan M.; Snow, Michael R.

doi:10.1021/ic00142a010

Cited by 28 publications

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“…Synthetic metal complexes can be used as simple model systems for such enzymes. To this purpose, several mononuclear Zn(II) complexes have been studied in order to analyze binding and activation of phosphate esters. − Although dinuclear complexes have been also used in model studies on hydrolysis of phosphate esters, most of these have been accomplished with metals such as Cu(II), Co(III), or La(III). − Dinuclear synthetic Zn(II) complexes able to hydrolyze phosphate esters are rare. Recently, Kimura and co-workers have reported a dinuclear Zn(II) complex with a propanol-bridged octaazacryptand able to selectively recognize and hydrolyze phosphate monoesters .…”

Section: Introductionmentioning

confidence: 99%

Carboxy and Phosphate Esters Cleavage with Mono- and Dinuclear Zinc(II) Macrocyclic Complexes in Aqueous Solution. Crystal Structure of [Zn₂L1(μ-PP)₂(MeOH)₂](ClO₄)₂ (L1 = [30]aneN₆O₄, PP^- = Diphenyl Phosphate)

et al. 1997

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The ligand [30]aneN(6)O(4) (L1) binds two Zn(II) in aqueous solution. The stability constants of the L1 complexes have been determined at 308.1 K by means of potentiometric measurements. Dinuclear monohydroxo [Zn(2)L1OH](3+) and dihydroxo [Zn(2)L1(OH)(2)](2+) complexes are formed in aqueous solution from neutral to alkaline pH. The kinetics of promoted hydrolysis of p-nitrophenyl acetate (NA) was studied. Both hydroxo species promote p-nitrophenyl acetate (NA) hydrolysis at 298.1 K with second-order kinetics. The activity of these species in NA hydrolysis is similar to that found for the mononuclear L2-Zn-OH(+) complex (L2 = [15]aneN(3)O(2)), indicating that the hydrolytic process takes place via a simple bimolecular mechanism. The hydrolysis rate of bis(p-nitrophenyl) phosphate (BNP) was measured in aqueous solution at 308.1 K in the presence of the L1and L2 zinc complexes. The hydrolysis rate of BNP is increased almost 10-fold by the dinuclear [Zn(2)L1(OH)(2)](2+) complex with respect to the mononuclear L2-Zn-OH(+) one. This result indicates a cooperative role of the two metals in the hydrolytic mechanism. A bridging coordination of the phosphate ester to the two Zn(II) ions can be suggested. The crystal structure of [Zn(2)L1(&mgr;-PP)(2)(MeOH)(2)](ClO(4))(2) (PP(-) = diphenyl phosphate) (space group P&onemacr;, a = 10.681(5) Å, b = 12.042(1) Å, c = 13.191(3) Å, alpha = 74.63(2) degrees, beta = 71.74(3) degrees, gamma = 68.41(2) degrees, V = 1476.4(8) Å(3), Z = 1, R = 0.0472, R(w)(2) = 0.1166) strongly supports this hypothesis, since in the [Zn(2)L1(&mgr;-PP)(2)(MeOH)(2)](2+) cation the diphosphate anions bridge the two metals. The dinuclear Zn(II) complexes of L1 provide a simple model system for hydrolytic dizinc enzymes.

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Section: Introductionmentioning

confidence: 99%

Carboxy and Phosphate Esters Cleavage with Mono- and Dinuclear Zinc(II) Macrocyclic Complexes in Aqueous Solution. Crystal Structure of [Zn₂L1(μ-PP)₂(MeOH)₂](ClO₄)₂ (L1 = [30]aneN₆O₄, PP^- = Diphenyl Phosphate)

et al. 1997

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“…Perhaps some of the most significant studies by the Sargeson group, and studies with the most relevance to many later efforts in modelling the mechanisms of metalloenzyme systems, were those of the hydrolysis of phosphate esters bound to cobalt(III) complexes carried out in the 1980s . In one study the hydrolysis of the 4‐nitrophenyl phosphate ester complex cis ‐[Co(en) 2 (OH)(O 3 POC 6 H 4 NO 2 )] was studied using both 31 P NMR spectroscopy, and by monitoring the release of nitrophenol at 400 nm, over the pH range 7–14.…”

Section: The Water Molecule and The Study Of The Hydrolysis Of Estementioning

confidence: 99%

Metal‐coordinated Hydroxide as a Nucleophile: a Brief History

Blackman

Gahan

2018

Zeitschrift anorg allge chemie

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It is well known that a metal‐bound hydroxido ligand is an efficient nucleophile around neutral pH. In a mechanistic sense, the presence and chemical reactivity of the coordinated hydroxido nucleophile are frequently invoked both in biomimetic chemistry and in numerous examples of hydrolytic metalloenzymes. In this review, we explore the background of this chemistry in order to attempt to trace the thinking which led to what is now a fully accepted mechanistic pathway.

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“…Mononuclear [13][14][15], binuclear [16][17][18][19][20][21][22][23][24][25][26][27], trinuclear [28][29], tetranuclear [30][31][32][33] and…”

Section: Introductionmentioning

confidence: 99%

Crystal structure and molecular stereochemistry of polymeric Cu2(DMP)4(DMSO) as a platform for phosphate diester binding

Rafizadeh¹,

Tayebee²,

Amani³

et al. 2006

Cryst. Res. Technol.

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Treatment of a solution of CuCl 2 in dimethyl phosphate (DMP) in an inert solvent under nitrogen atmosphere resulted in a light blue fluorescence powder. Slow evaporation of H 2 O-DMSO solution of this powder led to the formation of blue-sky crystals of a new polymeric Cu(II) complex, with a unit cell composed of Cu 2 (DMP) 4 (DMSO), (1). The crystal and molecular structure of the complex was established crystallographically. Compound (1) crystallizes in the monoclinic space group P2 1 /n with a = 12.8920(11)Å, b = 13.1966(11)Å, c = 14.7926(13)Å, α = 90°, β = 98.943(2)°, γ = 90° and Z = 4. A square pyramidal environment for the metal center is established by coordination of oxygen atoms of four bridging DMP ligands in the basal positions and a tri-centered oxygen atom of DMSO in the apical disposition. The sixth position is also affected by a weak interaction with the sulfur atom of DMSO. The phosphorous atom in the bridging DMP is arranged in a deformed tetrahedron with gg conformation for methyl esters with C 2v symmetry. Accordingly, the angles of methoxy substituents are unexpectedly smaller than the bridging oxygens, and synchronous z-in and z-out distortions are suggested for DMP anion. The oxygen atom of SOCuCu´ fragment derived from DMSO, functions as a tri-centered nuclei lie almost in a trigonal triangle environment. This study helps provide further insights into the binding nature of phosphate esters to the active sites of enzymes, which catalyze phosphoryl transfer reactions.

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Structure and synthesis of isomers of novel binuclear cobalt(III)-phenyl phosphate complexes

Cited by 28 publications

References 0 publications

Carboxy and Phosphate Esters Cleavage with Mono- and Dinuclear Zinc(II) Macrocyclic Complexes in Aqueous Solution. Crystal Structure of [Zn₂L1(μ-PP)₂(MeOH)₂](ClO₄)₂ (L1 = [30]aneN₆O₄, PP^- = Diphenyl Phosphate)

Carboxy and Phosphate Esters Cleavage with Mono- and Dinuclear Zinc(II) Macrocyclic Complexes in Aqueous Solution. Crystal Structure of [Zn₂L1(μ-PP)₂(MeOH)₂](ClO₄)₂ (L1 = [30]aneN₆O₄, PP^- = Diphenyl Phosphate)

Metal‐coordinated Hydroxide as a Nucleophile: a Brief History

Crystal structure and molecular stereochemistry of polymeric Cu2(DMP)4(DMSO) as a platform for phosphate diester binding

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Structure and synthesis of isomers of novel binuclear cobalt(III)-phenyl phosphate complexes

Cited by 28 publications

References 0 publications

Carboxy and Phosphate Esters Cleavage with Mono- and Dinuclear Zinc(II) Macrocyclic Complexes in Aqueous Solution. Crystal Structure of [Zn2L1(μ-PP)2(MeOH)2](ClO4)2 (L1 = [30]aneN6O4, PP- = Diphenyl Phosphate)

Carboxy and Phosphate Esters Cleavage with Mono- and Dinuclear Zinc(II) Macrocyclic Complexes in Aqueous Solution. Crystal Structure of [Zn2L1(μ-PP)2(MeOH)2](ClO4)2 (L1 = [30]aneN6O4, PP- = Diphenyl Phosphate)

Metal‐coordinated Hydroxide as a Nucleophile: a Brief History

Crystal structure and molecular stereochemistry of polymeric Cu2(DMP)4(DMSO) as a platform for phosphate diester binding

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Product

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Carboxy and Phosphate Esters Cleavage with Mono- and Dinuclear Zinc(II) Macrocyclic Complexes in Aqueous Solution. Crystal Structure of [Zn₂L1(μ-PP)₂(MeOH)₂](ClO₄)₂ (L1 = [30]aneN₆O₄, PP^- = Diphenyl Phosphate)

Carboxy and Phosphate Esters Cleavage with Mono- and Dinuclear Zinc(II) Macrocyclic Complexes in Aqueous Solution. Crystal Structure of [Zn₂L1(μ-PP)₂(MeOH)₂](ClO₄)₂ (L1 = [30]aneN₆O₄, PP^- = Diphenyl Phosphate)