Reaction pathways for Zn(II)-catalyzed carboxylic acid esters hydrolysis

被引：10

作者：

Bazzicalupi, C ^{[1
]}

Bencini, A ^{[1
]}

Berni, E ^{[1
]}

Di Vaira, M ^{[1
]}

机构：

[1] Univ Florence, Dept Chem, I-50019 Florence, Italy

来源：

INORGANICA CHIMICA ACTA | 2005年 / 358卷 / 01期

关键词：

ester hydrolysis; macrocyclic ligand; Zn(II) complexes; DFT; hydrolysis kinetics;

D O I：

10.1016/j.ica.2004.07.018

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction pathways have been investigated by quantum-mechanical procedures on gas phase models for the hydrolysis of methyl acetate catalyzed by a monohydroxo-Zn(II) complex formed by a phenanthroline-containing polyamine macrocycle. Based on consideration of energy barrier heights, the hydrolysis process is predicted to be bimolecular, consistently with kinetic data obtained for the hydrolysis of p-nitrophenyl acetate promoted by the modelled catalyst. Differences with respect to results of theoretical studies on the more extensively investigated hydrolysis processes catalyzed by the OH- anion are discussed and appear to be mostly due to the presence of the metal centre close to the OH function in the system now investigated. The pervasive presence and path-controlling role of hydrogen bonds are also discussed. (C) 2004 Elsevier B.V. All rights reserved.

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页码：77 / 92

页数：16

相关论文

共 72 条

[1] Polyaza[n]paracyclophanes as synthetic models of Zn containing enzymes. The role of a non coordinated nitrogen atom in the proximity of the metal [J].

Altava, B ;

Burguete, MI ;

Luis, SV ;

Miravet, JF ;

GarciaEspana, E ;

Marcelino, V ;

Soriano, C .

TETRAHEDRON, 1997, 53 (13) :4751-4762

[2]

[Anonymous], 1986, ZINC ENZYMES

[3]

[Anonymous], 1987, MECH THEORY ORGANIC

[4]

BAMFORD CH, 1972, ESTER FORMATION HYDR, V10

[5] CONCERTEDNESS IN ACYL GROUP TRANSFER IN SOLUTION - A SINGLE TRANSITION-STATE IN ACETYL GROUP TRANSFER BETWEEN PHENOLATE ION NUCLEOPHILES [J].

BASAIF, S ;

LUTHRA, AK ;

WILLIAMS, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (21) :6362-6368

[6] CONCERTED ACETYL GROUP TRANSFER BETWEEN SUBSTITUTED PHENOLATE ION NUCLEOPHILES - VARIATION OF TRANSITION-STATE STRUCTURE AS A FUNCTION OF SUBSTITUENT [J].

BASAIF, S ;

LUTHRA, AK ;

WILLIAMS, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (07) :2647-2652

[7] SINGLE TRANSITION-STATE IN THE TRANSFER OF A NEUTRAL PHOSPHORYL GROUP BETWEEN PHENOXIDE ION NUCLEOPHILES IN AQUEOUS-SOLUTION [J].

BASAIF, SA ;

WARING, MA ;

WILLIAMS, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (22) :8115-8120

[8] Effect of protonation and Zn(II) coordination on the fluorescence emission of a phenanthroline-containing macrocycle. An unusual case of "nonemissive'' Zn(II) complex [J].

Bazzicalupi, C ;

Bencini, A ;

Bianchi, A ;

Giorgi, C ;

Fusi, V ;

Valtancoli, B ;

Bernardo, MA ;

Pina, F .

INORGANIC CHEMISTRY, 1999, 38 (17) :3806-3813

[9] Carboxy and phosphate esters cleavage with mono- and dinuclear zinc(II) macrocyclic complexes in aqueous solution, crystal structure of [Zn(2)L1(mu-PP)(2)(MeOH)(2)](ClO4)(2) (L1=[30]aneN(6)O(4), PP- equals diphenyl phosphate) [J].

Bazzicalupi, C ;

Bencini, A ;

Bianchi, A ;

Fusi, V ;

Giorgi, C ;

Paoletti, P ;

Valtancoli, B ;

Zanchi, D .

INORGANIC CHEMISTRY, 1997, 36 (13) :2784-2790

[10] Polyamine macrocycles incorporating a phenanthroline unit: Their synthesis, basicity, and Cu(II) coordination [J].

Bazzicalupi, C ;

Bencini, A ;

Fusi, V ;

Giorgi, C ;

Paoletti, P ;

Valtancoli, B .

INORGANIC CHEMISTRY, 1998, 37 (05) :941-948

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