Crystal structure, solution properties and hydrolytic activity of an alkoxo-bridged dinuclear copper(II) complex, as a ribonuclease model

T. Gajda, A. Jancsó, Satu Mikkola, Harri Lönnberg, Holger Sirges

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Abstract

Crystal structures, solution properties and ribonuclease activity of copper(II) complexes of a binucleating, bis-pyridyl ligand (N,N′-bis(2-pyridylmethyl)-1,3-diaminopropan-2-ol, L) have been investigated. The single-crystal X-ray structure of the mononuclear complex [CuL(ClO4)2] (1) shows distorted octahedral geometry around the metal ion, with the four nitrogens of the ligand in the equatorial plane of copper(II). A μ-alkoxo-bridged dinuclear complex is formed in the presence of a two-fold metal excess. Despite the symmetrical ligand, the two metal ions in [Cu2(LH-1)(DPP)(ClO4)(CH3OH)]ClO 4 (2, DPP = diphenyl phosphate) have distinct, distorted octahedral (Cu1) and square pyramidal (Cu2) geometry. Beside the alkoxo-oxygen, the phosphate group of DPP also bridges the two metal centers in 2 in a μ-1,3-bridging mode. The complexes formed in aqueous solution are likely to have analogous structures to 1 and 2. The dinuclear [Cu2(LH-1)(OH)] complex efficiently promotes the hydrolysis/transesterification of both activated (2-hydroxypropyl p-nitrophenyl phosphate, hpnp) and non-activated, biological phosphodiesters (uridine-2′,3′-cyclic-monophosphate, cUMP and uridylyl-(3′,5′)-uridine, UpU). For example, a 2 mM solution of the dinuclear complex provides 5 orders of magnitude acceleration in the hydrolysis of cUMP. The proposed mechanisms include double Lewis-acid activation with intramolecular general base catalysis.

Original languageEnglish
Pages (from-to)1757-1763
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number8
Publication statusPublished - 2002

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Ribonucleases
Copper
Crystal structure
Uridine
Ligands
Metal ions
Hydrolysis
Metals
Phosphates
Lewis Acids
Geometry
Transesterification
Catalysis
Nitrogen
Chemical activation
Single crystals
Oxygen
X rays
LH 1
cyclic 3',5'-uridine monophosphate

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Crystal structure, solution properties and hydrolytic activity of an alkoxo-bridged dinuclear copper(II) complex, as a ribonuclease model",
abstract = "Crystal structures, solution properties and ribonuclease activity of copper(II) complexes of a binucleating, bis-pyridyl ligand (N,N′-bis(2-pyridylmethyl)-1,3-diaminopropan-2-ol, L) have been investigated. The single-crystal X-ray structure of the mononuclear complex [CuL(ClO4)2] (1) shows distorted octahedral geometry around the metal ion, with the four nitrogens of the ligand in the equatorial plane of copper(II). A μ-alkoxo-bridged dinuclear complex is formed in the presence of a two-fold metal excess. Despite the symmetrical ligand, the two metal ions in [Cu2(LH-1)(DPP)(ClO4)(CH3OH)]ClO 4 (2, DPP = diphenyl phosphate) have distinct, distorted octahedral (Cu1) and square pyramidal (Cu2) geometry. Beside the alkoxo-oxygen, the phosphate group of DPP also bridges the two metal centers in 2 in a μ-1,3-bridging mode. The complexes formed in aqueous solution are likely to have analogous structures to 1 and 2. The dinuclear [Cu2(LH-1)(OH)] complex efficiently promotes the hydrolysis/transesterification of both activated (2-hydroxypropyl p-nitrophenyl phosphate, hpnp) and non-activated, biological phosphodiesters (uridine-2′,3′-cyclic-monophosphate, cUMP and uridylyl-(3′,5′)-uridine, UpU). For example, a 2 mM solution of the dinuclear complex provides 5 orders of magnitude acceleration in the hydrolysis of cUMP. The proposed mechanisms include double Lewis-acid activation with intramolecular general base catalysis.",
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T1 - Crystal structure, solution properties and hydrolytic activity of an alkoxo-bridged dinuclear copper(II) complex, as a ribonuclease model

AU - Gajda, T.

AU - Jancsó, A.

AU - Mikkola, Satu

AU - Lönnberg, Harri

AU - Sirges, Holger

PY - 2002

Y1 - 2002

N2 - Crystal structures, solution properties and ribonuclease activity of copper(II) complexes of a binucleating, bis-pyridyl ligand (N,N′-bis(2-pyridylmethyl)-1,3-diaminopropan-2-ol, L) have been investigated. The single-crystal X-ray structure of the mononuclear complex [CuL(ClO4)2] (1) shows distorted octahedral geometry around the metal ion, with the four nitrogens of the ligand in the equatorial plane of copper(II). A μ-alkoxo-bridged dinuclear complex is formed in the presence of a two-fold metal excess. Despite the symmetrical ligand, the two metal ions in [Cu2(LH-1)(DPP)(ClO4)(CH3OH)]ClO 4 (2, DPP = diphenyl phosphate) have distinct, distorted octahedral (Cu1) and square pyramidal (Cu2) geometry. Beside the alkoxo-oxygen, the phosphate group of DPP also bridges the two metal centers in 2 in a μ-1,3-bridging mode. The complexes formed in aqueous solution are likely to have analogous structures to 1 and 2. The dinuclear [Cu2(LH-1)(OH)] complex efficiently promotes the hydrolysis/transesterification of both activated (2-hydroxypropyl p-nitrophenyl phosphate, hpnp) and non-activated, biological phosphodiesters (uridine-2′,3′-cyclic-monophosphate, cUMP and uridylyl-(3′,5′)-uridine, UpU). For example, a 2 mM solution of the dinuclear complex provides 5 orders of magnitude acceleration in the hydrolysis of cUMP. The proposed mechanisms include double Lewis-acid activation with intramolecular general base catalysis.

AB - Crystal structures, solution properties and ribonuclease activity of copper(II) complexes of a binucleating, bis-pyridyl ligand (N,N′-bis(2-pyridylmethyl)-1,3-diaminopropan-2-ol, L) have been investigated. The single-crystal X-ray structure of the mononuclear complex [CuL(ClO4)2] (1) shows distorted octahedral geometry around the metal ion, with the four nitrogens of the ligand in the equatorial plane of copper(II). A μ-alkoxo-bridged dinuclear complex is formed in the presence of a two-fold metal excess. Despite the symmetrical ligand, the two metal ions in [Cu2(LH-1)(DPP)(ClO4)(CH3OH)]ClO 4 (2, DPP = diphenyl phosphate) have distinct, distorted octahedral (Cu1) and square pyramidal (Cu2) geometry. Beside the alkoxo-oxygen, the phosphate group of DPP also bridges the two metal centers in 2 in a μ-1,3-bridging mode. The complexes formed in aqueous solution are likely to have analogous structures to 1 and 2. The dinuclear [Cu2(LH-1)(OH)] complex efficiently promotes the hydrolysis/transesterification of both activated (2-hydroxypropyl p-nitrophenyl phosphate, hpnp) and non-activated, biological phosphodiesters (uridine-2′,3′-cyclic-monophosphate, cUMP and uridylyl-(3′,5′)-uridine, UpU). For example, a 2 mM solution of the dinuclear complex provides 5 orders of magnitude acceleration in the hydrolysis of cUMP. The proposed mechanisms include double Lewis-acid activation with intramolecular general base catalysis.

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