[1H, 15N] Heteronuclear Single Quantum Coherence NMR Study of the Mechanism of Aquation of Platinum(IV) Ammine Complexes

M.S. Davies, M.D. Hall, Susan Berners-Price, T.W. Hambley

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Abstract

The aquation and hydrolysis of a series of platinum(IV) complexes of the general form cis, trans, cis-[PtCl2(X)(2)((NH3)-N-15)(2)] (X = Cl-, O2CCH3-, OH-) have been followed by [H-1, N-15] Heteronuclear Single Quantum Coherence NMR spectroscopy. Negligible aquation (<5%) is observed for the complexes where X = O2CCH3- or OH- over 3-4 weeks. Aquation of cis-[PtCl4((NH3)-N-15)(2)] (1) is observed, and the rate of aquation increases with increasing pH and upon the addition of 0.01 mol equiv of the platinum(II) complex cis-[PtCl2((NH3)-N-15)(2)] (cisplatin). The first aquated species formed from cis-[PtCl4(NH3)(2)] has one of the axial chloro groups (relative to the equatorial NH3 ligands) replaced by an aqua/hydroxo ligand. The second observed substitution occurs in an equatorial position. Peaks that are consistent with five of the eight possible aquation species were observed in the NMR spectra.
Original languageEnglish
Pages (from-to)7673-7680
JournalInorganic Chemistry
Volume47
Issue number17
DOIs
Publication statusPublished - 2008

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ammines
Platinum
platinum
Nuclear magnetic resonance
Ligands
nuclear magnetic resonance
ligands
Cisplatin
Nuclear magnetic resonance spectroscopy
hydrolysis
Hydrolysis
Substitution reactions
substitutes
spectroscopy
platinum tetrachloride

Cite this

Davies, M.S. ; Hall, M.D. ; Berners-Price, Susan ; Hambley, T.W. / [1H, 15N] Heteronuclear Single Quantum Coherence NMR Study of the Mechanism of Aquation of Platinum(IV) Ammine Complexes. In: Inorganic Chemistry. 2008 ; Vol. 47, No. 17. pp. 7673-7680.
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abstract = "The aquation and hydrolysis of a series of platinum(IV) complexes of the general form cis, trans, cis-[PtCl2(X)(2)((NH3)-N-15)(2)] (X = Cl-, O2CCH3-, OH-) have been followed by [H-1, N-15] Heteronuclear Single Quantum Coherence NMR spectroscopy. Negligible aquation (<5{\%}) is observed for the complexes where X = O2CCH3- or OH- over 3-4 weeks. Aquation of cis-[PtCl4((NH3)-N-15)(2)] (1) is observed, and the rate of aquation increases with increasing pH and upon the addition of 0.01 mol equiv of the platinum(II) complex cis-[PtCl2((NH3)-N-15)(2)] (cisplatin). The first aquated species formed from cis-[PtCl4(NH3)(2)] has one of the axial chloro groups (relative to the equatorial NH3 ligands) replaced by an aqua/hydroxo ligand. The second observed substitution occurs in an equatorial position. Peaks that are consistent with five of the eight possible aquation species were observed in the NMR spectra.",
author = "M.S. Davies and M.D. Hall and Susan Berners-Price and T.W. Hambley",
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[1H, 15N] Heteronuclear Single Quantum Coherence NMR Study of the Mechanism of Aquation of Platinum(IV) Ammine Complexes. / Davies, M.S.; Hall, M.D.; Berners-Price, Susan; Hambley, T.W.

In: Inorganic Chemistry, Vol. 47, No. 17, 2008, p. 7673-7680.

Research output: Contribution to journalArticle

TY - JOUR

T1 - [1H, 15N] Heteronuclear Single Quantum Coherence NMR Study of the Mechanism of Aquation of Platinum(IV) Ammine Complexes

AU - Davies, M.S.

AU - Hall, M.D.

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AU - Hambley, T.W.

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N2 - The aquation and hydrolysis of a series of platinum(IV) complexes of the general form cis, trans, cis-[PtCl2(X)(2)((NH3)-N-15)(2)] (X = Cl-, O2CCH3-, OH-) have been followed by [H-1, N-15] Heteronuclear Single Quantum Coherence NMR spectroscopy. Negligible aquation (<5%) is observed for the complexes where X = O2CCH3- or OH- over 3-4 weeks. Aquation of cis-[PtCl4((NH3)-N-15)(2)] (1) is observed, and the rate of aquation increases with increasing pH and upon the addition of 0.01 mol equiv of the platinum(II) complex cis-[PtCl2((NH3)-N-15)(2)] (cisplatin). The first aquated species formed from cis-[PtCl4(NH3)(2)] has one of the axial chloro groups (relative to the equatorial NH3 ligands) replaced by an aqua/hydroxo ligand. The second observed substitution occurs in an equatorial position. Peaks that are consistent with five of the eight possible aquation species were observed in the NMR spectra.

AB - The aquation and hydrolysis of a series of platinum(IV) complexes of the general form cis, trans, cis-[PtCl2(X)(2)((NH3)-N-15)(2)] (X = Cl-, O2CCH3-, OH-) have been followed by [H-1, N-15] Heteronuclear Single Quantum Coherence NMR spectroscopy. Negligible aquation (<5%) is observed for the complexes where X = O2CCH3- or OH- over 3-4 weeks. Aquation of cis-[PtCl4((NH3)-N-15)(2)] (1) is observed, and the rate of aquation increases with increasing pH and upon the addition of 0.01 mol equiv of the platinum(II) complex cis-[PtCl2((NH3)-N-15)(2)] (cisplatin). The first aquated species formed from cis-[PtCl4(NH3)(2)] has one of the axial chloro groups (relative to the equatorial NH3 ligands) replaced by an aqua/hydroxo ligand. The second observed substitution occurs in an equatorial position. Peaks that are consistent with five of the eight possible aquation species were observed in the NMR spectra.

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