Highly efficient phosphodiester hydrolysis promoted by a dinuclear copper(II) complex

T. Gajda, Y. Düpre, I. Török, J. Harmer, A. Schweiger, J. Sander, D. Kuppert, K. Hegetschweiler

Research output: Contribution to journalArticle

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Abstract

The interaction of CuII with the ligand tdci (1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol) was studied both in the solid state and in solution. The complexes that were formed were also tested for phosphoesterase activity. The pentanuclear complex [Cu5(tdciH-2)(tdci)2(OH)2 (NO3)2] (NO3)4·6H2O consists of two dinuclear units and one trinuclear unit, having two shared copper(II) ions. The metal centers within the pentanuclear structure have three distinct coordination environments. All five copper(II) ions are linked by hydroxo/alkoxo bridges forming a Cu5O6 cage. The Cu-Cu separations of the bridged centers are between 2.916 and 3.782 Å, while those of the nonbridged metal ions are 5.455-5.712 Å. The solution equilibria in the Cu11-tdci system proved to be extremely complicated. Depending on the pH and metal-to-ligand ratio, several differently deprotonated mono-, di-, and trinuclear complexes are formed. Their presence in solution was supported by mass, CW, and pulse EPR spectroscopic study, too. In these complexes, the metal ions are presumed to occupy tridentate {Oax,Neq,Oax} coordination sites and the O-donors of tdci may serve as bridging units between two metal ions. Additionally, deprotonation of the metal-bound water molecules may occur. The dinuclear Cu2LH-3 species, formed around pH 8.5, provides outstanding rate acceleration for the hydrolysis of the activated phosphodiester bis(4-nitrophenyl)-phosphate (BNPP). The second-order rate constant of BNPP hydrolysis promoted by the dinuclear complex (T = 298 K) is 0.95 M-1 s-1, which is ca. 47600-fold higher than that of the hydroxide ion catalyzed hydrolysis (kOH). Its activity is selective for the phosphodiester, and the hydrolysis was proved to be catalytic. The proposed bifunctional mechanism of the hydrolysis includes double Lewis acid activation and intramolecular nucleophilic catalysis.

Original languageEnglish
Pages (from-to)4918-4927
Number of pages10
JournalInorganic Chemistry
Volume40
Issue number19
DOIs
Publication statusPublished - Sep 10 2001

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hydrolysis
Copper
Hydrolysis
copper
Metal ions
metal ions
Metals
phosphates
metals
Ions
inositols
Ligands
Lewis Acids
Deprotonation
ions
ligands
Catalysis
hydroxides
catalysis
Paramagnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Gajda, T., Düpre, Y., Török, I., Harmer, J., Schweiger, A., Sander, J., ... Hegetschweiler, K. (2001). Highly efficient phosphodiester hydrolysis promoted by a dinuclear copper(II) complex. Inorganic Chemistry, 40(19), 4918-4927. https://doi.org/10.1021/ic0005902

Highly efficient phosphodiester hydrolysis promoted by a dinuclear copper(II) complex. / Gajda, T.; Düpre, Y.; Török, I.; Harmer, J.; Schweiger, A.; Sander, J.; Kuppert, D.; Hegetschweiler, K.

In: Inorganic Chemistry, Vol. 40, No. 19, 10.09.2001, p. 4918-4927.

Research output: Contribution to journalArticle

Gajda, T, Düpre, Y, Török, I, Harmer, J, Schweiger, A, Sander, J, Kuppert, D & Hegetschweiler, K 2001, 'Highly efficient phosphodiester hydrolysis promoted by a dinuclear copper(II) complex', Inorganic Chemistry, vol. 40, no. 19, pp. 4918-4927. https://doi.org/10.1021/ic0005902
Gajda T, Düpre Y, Török I, Harmer J, Schweiger A, Sander J et al. Highly efficient phosphodiester hydrolysis promoted by a dinuclear copper(II) complex. Inorganic Chemistry. 2001 Sep 10;40(19):4918-4927. https://doi.org/10.1021/ic0005902
Gajda, T. ; Düpre, Y. ; Török, I. ; Harmer, J. ; Schweiger, A. ; Sander, J. ; Kuppert, D. ; Hegetschweiler, K. / Highly efficient phosphodiester hydrolysis promoted by a dinuclear copper(II) complex. In: Inorganic Chemistry. 2001 ; Vol. 40, No. 19. pp. 4918-4927.
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abstract = "The interaction of CuII with the ligand tdci (1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol) was studied both in the solid state and in solution. The complexes that were formed were also tested for phosphoesterase activity. The pentanuclear complex [Cu5(tdciH-2)(tdci)2(OH)2 (NO3)2] (NO3)4·6H2O consists of two dinuclear units and one trinuclear unit, having two shared copper(II) ions. The metal centers within the pentanuclear structure have three distinct coordination environments. All five copper(II) ions are linked by hydroxo/alkoxo bridges forming a Cu5O6 cage. The Cu-Cu separations of the bridged centers are between 2.916 and 3.782 {\AA}, while those of the nonbridged metal ions are 5.455-5.712 {\AA}. The solution equilibria in the Cu11-tdci system proved to be extremely complicated. Depending on the pH and metal-to-ligand ratio, several differently deprotonated mono-, di-, and trinuclear complexes are formed. Their presence in solution was supported by mass, CW, and pulse EPR spectroscopic study, too. In these complexes, the metal ions are presumed to occupy tridentate {Oax,Neq,Oax} coordination sites and the O-donors of tdci may serve as bridging units between two metal ions. Additionally, deprotonation of the metal-bound water molecules may occur. The dinuclear Cu2LH-3 species, formed around pH 8.5, provides outstanding rate acceleration for the hydrolysis of the activated phosphodiester bis(4-nitrophenyl)-phosphate (BNPP). The second-order rate constant of BNPP hydrolysis promoted by the dinuclear complex (T = 298 K) is 0.95 M-1 s-1, which is ca. 47600-fold higher than that of the hydroxide ion catalyzed hydrolysis (kOH). Its activity is selective for the phosphodiester, and the hydrolysis was proved to be catalytic. The proposed bifunctional mechanism of the hydrolysis includes double Lewis acid activation and intramolecular nucleophilic catalysis.",
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AU - Düpre, Y.

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AU - Harmer, J.

AU - Schweiger, A.

AU - Sander, J.

AU - Kuppert, D.

AU - Hegetschweiler, K.

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N2 - The interaction of CuII with the ligand tdci (1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol) was studied both in the solid state and in solution. The complexes that were formed were also tested for phosphoesterase activity. The pentanuclear complex [Cu5(tdciH-2)(tdci)2(OH)2 (NO3)2] (NO3)4·6H2O consists of two dinuclear units and one trinuclear unit, having two shared copper(II) ions. The metal centers within the pentanuclear structure have three distinct coordination environments. All five copper(II) ions are linked by hydroxo/alkoxo bridges forming a Cu5O6 cage. The Cu-Cu separations of the bridged centers are between 2.916 and 3.782 Å, while those of the nonbridged metal ions are 5.455-5.712 Å. The solution equilibria in the Cu11-tdci system proved to be extremely complicated. Depending on the pH and metal-to-ligand ratio, several differently deprotonated mono-, di-, and trinuclear complexes are formed. Their presence in solution was supported by mass, CW, and pulse EPR spectroscopic study, too. In these complexes, the metal ions are presumed to occupy tridentate {Oax,Neq,Oax} coordination sites and the O-donors of tdci may serve as bridging units between two metal ions. Additionally, deprotonation of the metal-bound water molecules may occur. The dinuclear Cu2LH-3 species, formed around pH 8.5, provides outstanding rate acceleration for the hydrolysis of the activated phosphodiester bis(4-nitrophenyl)-phosphate (BNPP). The second-order rate constant of BNPP hydrolysis promoted by the dinuclear complex (T = 298 K) is 0.95 M-1 s-1, which is ca. 47600-fold higher than that of the hydroxide ion catalyzed hydrolysis (kOH). Its activity is selective for the phosphodiester, and the hydrolysis was proved to be catalytic. The proposed bifunctional mechanism of the hydrolysis includes double Lewis acid activation and intramolecular nucleophilic catalysis.

AB - The interaction of CuII with the ligand tdci (1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol) was studied both in the solid state and in solution. The complexes that were formed were also tested for phosphoesterase activity. The pentanuclear complex [Cu5(tdciH-2)(tdci)2(OH)2 (NO3)2] (NO3)4·6H2O consists of two dinuclear units and one trinuclear unit, having two shared copper(II) ions. The metal centers within the pentanuclear structure have three distinct coordination environments. All five copper(II) ions are linked by hydroxo/alkoxo bridges forming a Cu5O6 cage. The Cu-Cu separations of the bridged centers are between 2.916 and 3.782 Å, while those of the nonbridged metal ions are 5.455-5.712 Å. The solution equilibria in the Cu11-tdci system proved to be extremely complicated. Depending on the pH and metal-to-ligand ratio, several differently deprotonated mono-, di-, and trinuclear complexes are formed. Their presence in solution was supported by mass, CW, and pulse EPR spectroscopic study, too. In these complexes, the metal ions are presumed to occupy tridentate {Oax,Neq,Oax} coordination sites and the O-donors of tdci may serve as bridging units between two metal ions. Additionally, deprotonation of the metal-bound water molecules may occur. The dinuclear Cu2LH-3 species, formed around pH 8.5, provides outstanding rate acceleration for the hydrolysis of the activated phosphodiester bis(4-nitrophenyl)-phosphate (BNPP). The second-order rate constant of BNPP hydrolysis promoted by the dinuclear complex (T = 298 K) is 0.95 M-1 s-1, which is ca. 47600-fold higher than that of the hydroxide ion catalyzed hydrolysis (kOH). Its activity is selective for the phosphodiester, and the hydrolysis was proved to be catalytic. The proposed bifunctional mechanism of the hydrolysis includes double Lewis acid activation and intramolecular nucleophilic catalysis.

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