Mechanism of water exchange onfive-coordinate copper(II) complexes

Anton Neubrand, Florian Thaler, Manuela Körner, Achim Zahl, Colin D. Hubbard, Rudi Van Eldik

Research output: Contribution to journalArticle

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Abstract

The effects of temperature and pressure on the water exchange reaction of the five-coordinate complexes [Cu(tmpa)(H2O)]2+ and [Cu(fz)2(H2O)]2- (tmpa = tris(2-pyridylmethyl)amine; fz = ferrozine = 5,6-bis(4-sulfonatophenyl)-3-(2-pyridyl)-1,2,4-triazine) were studied by employing 17O NMR spectroscopy. The former compound shows a solvent exchange rate constant kex of (8.6 ± 0.4) × 106 s-1 at 298 K and ambient pressure, within a factor of three of that for the corresponding process for [Cu(tren)(H2O)]2+ (tren = 2,2′2″-triaminotriethylamine). The activation parameters ΔH#, ΔS# and ΔV# for the reaction are 43.0 ± 1.5 kJ mol-1, +32 ± 6 J K-1 mol-1 and -3.0 ± 0.1 cm3 mol-1, respectively. For [Cu(fz)2(H2O)]2-, kex is (3.5 ± 2.6) × 105 s-1 at 298 K and ambient presure, which is about an order of magnitude less than for [Cu(tren)(H2O)]2+. The ΔH#, ΔS# and ΔV# values for the water exchange are 25.9 ± 2.2 kJ mol-1, -52 ± 7 J K-1 mol-1 and -4.7 ± 0.2 cm3 mol-1. The activation volume is modestly negative for both reactions and therefore implies an associative interchange (Ia) mechanism. The results are discussed in reference to data for water exchange reactions of Cu(II) complexes available from the literature.

Original languageEnglish
Pages (from-to)957-961
Number of pages5
JournalJournal of the Chemical Society, Dalton Transactions
Issue number6
Publication statusPublished - 2002

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Copper
Water
Ferrozine
Chemical activation
Interchanges
Nuclear magnetic resonance spectroscopy
Rate constants
Temperature
tris(2-aminoethyl)amine
tris(2-pyridylmethyl)amine
1,2,4-triazine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Neubrand, A., Thaler, F., Körner, M., Zahl, A., Hubbard, C. D., & Van Eldik, R. (2002). Mechanism of water exchange onfive-coordinate copper(II) complexes. Journal of the Chemical Society, Dalton Transactions, (6), 957-961.

Mechanism of water exchange onfive-coordinate copper(II) complexes. / Neubrand, Anton; Thaler, Florian; Körner, Manuela; Zahl, Achim; Hubbard, Colin D.; Van Eldik, Rudi.

In: Journal of the Chemical Society, Dalton Transactions, No. 6, 2002, p. 957-961.

Research output: Contribution to journalArticle

Neubrand, A, Thaler, F, Körner, M, Zahl, A, Hubbard, CD & Van Eldik, R 2002, 'Mechanism of water exchange onfive-coordinate copper(II) complexes', Journal of the Chemical Society, Dalton Transactions, no. 6, pp. 957-961.
Neubrand A, Thaler F, Körner M, Zahl A, Hubbard CD, Van Eldik R. Mechanism of water exchange onfive-coordinate copper(II) complexes. Journal of the Chemical Society, Dalton Transactions. 2002;(6):957-961.
Neubrand, Anton ; Thaler, Florian ; Körner, Manuela ; Zahl, Achim ; Hubbard, Colin D. ; Van Eldik, Rudi. / Mechanism of water exchange onfive-coordinate copper(II) complexes. In: Journal of the Chemical Society, Dalton Transactions. 2002 ; No. 6. pp. 957-961.
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N2 - The effects of temperature and pressure on the water exchange reaction of the five-coordinate complexes [Cu(tmpa)(H2O)]2+ and [Cu(fz)2(H2O)]2- (tmpa = tris(2-pyridylmethyl)amine; fz = ferrozine = 5,6-bis(4-sulfonatophenyl)-3-(2-pyridyl)-1,2,4-triazine) were studied by employing 17O NMR spectroscopy. The former compound shows a solvent exchange rate constant kex of (8.6 ± 0.4) × 106 s-1 at 298 K and ambient pressure, within a factor of three of that for the corresponding process for [Cu(tren)(H2O)]2+ (tren = 2,2′2″-triaminotriethylamine). The activation parameters ΔH#, ΔS# and ΔV# for the reaction are 43.0 ± 1.5 kJ mol-1, +32 ± 6 J K-1 mol-1 and -3.0 ± 0.1 cm3 mol-1, respectively. For [Cu(fz)2(H2O)]2-, kex is (3.5 ± 2.6) × 105 s-1 at 298 K and ambient presure, which is about an order of magnitude less than for [Cu(tren)(H2O)]2+. The ΔH#, ΔS# and ΔV# values for the water exchange are 25.9 ± 2.2 kJ mol-1, -52 ± 7 J K-1 mol-1 and -4.7 ± 0.2 cm3 mol-1. The activation volume is modestly negative for both reactions and therefore implies an associative interchange (Ia) mechanism. The results are discussed in reference to data for water exchange reactions of Cu(II) complexes available from the literature.

AB - The effects of temperature and pressure on the water exchange reaction of the five-coordinate complexes [Cu(tmpa)(H2O)]2+ and [Cu(fz)2(H2O)]2- (tmpa = tris(2-pyridylmethyl)amine; fz = ferrozine = 5,6-bis(4-sulfonatophenyl)-3-(2-pyridyl)-1,2,4-triazine) were studied by employing 17O NMR spectroscopy. The former compound shows a solvent exchange rate constant kex of (8.6 ± 0.4) × 106 s-1 at 298 K and ambient pressure, within a factor of three of that for the corresponding process for [Cu(tren)(H2O)]2+ (tren = 2,2′2″-triaminotriethylamine). The activation parameters ΔH#, ΔS# and ΔV# for the reaction are 43.0 ± 1.5 kJ mol-1, +32 ± 6 J K-1 mol-1 and -3.0 ± 0.1 cm3 mol-1, respectively. For [Cu(fz)2(H2O)]2-, kex is (3.5 ± 2.6) × 105 s-1 at 298 K and ambient presure, which is about an order of magnitude less than for [Cu(tren)(H2O)]2+. The ΔH#, ΔS# and ΔV# values for the water exchange are 25.9 ± 2.2 kJ mol-1, -52 ± 7 J K-1 mol-1 and -4.7 ± 0.2 cm3 mol-1. The activation volume is modestly negative for both reactions and therefore implies an associative interchange (Ia) mechanism. The results are discussed in reference to data for water exchange reactions of Cu(II) complexes available from the literature.

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