[1H,15N] NMR studies of the aquation of cis-diamine platinum(II) complexes

L. Cubo, Donald Thomas, J. Zhang, A.G. Quiroga, C. Navarro-Ranninger, Susan Berners-Price

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Abstract

Two 15N-labelled cis-Pt(II) diamine complexes with dimethylamine (15N-dma) and isopropylamine (15N-ipa) ligands have been prepared and characterised. [1H,15N] HSQC NMR spectroscopy is used to obtain the rate and equilibrium constants for the aquation of cis-[PtCl2(15N-dma)2] at 298 K in 0.1 M NaClO4 and to determine the pKa values of cis-[PtCl(H2O)(15N-dma)2]+ (6.37) and cis-[Pt(H2O)2(15N-dma)2]2+ (pKa1 = 5.17, pKa2 = 6.47). The rate constants for the first and second aquation steps (k1 = (2.12 ± 0.01) × 10−5 s−1, k2 = (8.7 ± 0.7) × 10−6 s−1) and anation steps (k−1 = (6.7 ± 0.8) × 10−3 M−1 s−1, k−2 = 0.043 ± 0.004 M−1 s−1) are very similar to those reported for cisplatin under similar conditions, and a minor difference is that slow formation of the hydroxo-bridged dimer is observed. Aquation studies of cis-[PtCl2(15N-ipa)2] were precluded by the close proximity of the NH proton signal to the 1H2O resonance.
Original languageEnglish
Pages (from-to)1022-1026
JournalInorganica Chimica Acta
Volume362
Issue number3
DOIs
Publication statusPublished - 2009

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Diamines
diamines
Platinum
Rate constants
platinum
Nuclear magnetic resonance
nuclear magnetic resonance
Equilibrium constants
Dimers
Cisplatin
Nuclear magnetic resonance spectroscopy
Protons
proximity
Ligands
dimers
ligands
protons
spectroscopy
2-propylamine
dimethylamine

Cite this

Cubo, L., Thomas, D., Zhang, J., Quiroga, A. G., Navarro-Ranninger, C., & Berners-Price, S. (2009). [1H,15N] NMR studies of the aquation of cis-diamine platinum(II) complexes. Inorganica Chimica Acta, 362(3), 1022-1026. https://doi.org/10.1016/j.ica.2008.03.117
Cubo, L. ; Thomas, Donald ; Zhang, J. ; Quiroga, A.G. ; Navarro-Ranninger, C. ; Berners-Price, Susan. / [1H,15N] NMR studies of the aquation of cis-diamine platinum(II) complexes. In: Inorganica Chimica Acta. 2009 ; Vol. 362, No. 3. pp. 1022-1026.
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abstract = "Two 15N-labelled cis-Pt(II) diamine complexes with dimethylamine (15N-dma) and isopropylamine (15N-ipa) ligands have been prepared and characterised. [1H,15N] HSQC NMR spectroscopy is used to obtain the rate and equilibrium constants for the aquation of cis-[PtCl2(15N-dma)2] at 298 K in 0.1 M NaClO4 and to determine the pKa values of cis-[PtCl(H2O)(15N-dma)2]+ (6.37) and cis-[Pt(H2O)2(15N-dma)2]2+ (pKa1 = 5.17, pKa2 = 6.47). The rate constants for the first and second aquation steps (k1 = (2.12 ± 0.01) × 10−5 s−1, k2 = (8.7 ± 0.7) × 10−6 s−1) and anation steps (k−1 = (6.7 ± 0.8) × 10−3 M−1 s−1, k−2 = 0.043 ± 0.004 M−1 s−1) are very similar to those reported for cisplatin under similar conditions, and a minor difference is that slow formation of the hydroxo-bridged dimer is observed. Aquation studies of cis-[PtCl2(15N-ipa)2] were precluded by the close proximity of the NH proton signal to the 1H2O resonance.",
author = "L. Cubo and Donald Thomas and J. Zhang and A.G. Quiroga and C. Navarro-Ranninger and Susan Berners-Price",
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Cubo, L, Thomas, D, Zhang, J, Quiroga, AG, Navarro-Ranninger, C & Berners-Price, S 2009, '[1H,15N] NMR studies of the aquation of cis-diamine platinum(II) complexes' Inorganica Chimica Acta, vol. 362, no. 3, pp. 1022-1026. https://doi.org/10.1016/j.ica.2008.03.117

[1H,15N] NMR studies of the aquation of cis-diamine platinum(II) complexes. / Cubo, L.; Thomas, Donald; Zhang, J.; Quiroga, A.G.; Navarro-Ranninger, C.; Berners-Price, Susan.

In: Inorganica Chimica Acta, Vol. 362, No. 3, 2009, p. 1022-1026.

Research output: Contribution to journalArticle

TY - JOUR

T1 - [1H,15N] NMR studies of the aquation of cis-diamine platinum(II) complexes

AU - Cubo, L.

AU - Thomas, Donald

AU - Zhang, J.

AU - Quiroga, A.G.

AU - Navarro-Ranninger, C.

AU - Berners-Price, Susan

PY - 2009

Y1 - 2009

N2 - Two 15N-labelled cis-Pt(II) diamine complexes with dimethylamine (15N-dma) and isopropylamine (15N-ipa) ligands have been prepared and characterised. [1H,15N] HSQC NMR spectroscopy is used to obtain the rate and equilibrium constants for the aquation of cis-[PtCl2(15N-dma)2] at 298 K in 0.1 M NaClO4 and to determine the pKa values of cis-[PtCl(H2O)(15N-dma)2]+ (6.37) and cis-[Pt(H2O)2(15N-dma)2]2+ (pKa1 = 5.17, pKa2 = 6.47). The rate constants for the first and second aquation steps (k1 = (2.12 ± 0.01) × 10−5 s−1, k2 = (8.7 ± 0.7) × 10−6 s−1) and anation steps (k−1 = (6.7 ± 0.8) × 10−3 M−1 s−1, k−2 = 0.043 ± 0.004 M−1 s−1) are very similar to those reported for cisplatin under similar conditions, and a minor difference is that slow formation of the hydroxo-bridged dimer is observed. Aquation studies of cis-[PtCl2(15N-ipa)2] were precluded by the close proximity of the NH proton signal to the 1H2O resonance.

AB - Two 15N-labelled cis-Pt(II) diamine complexes with dimethylamine (15N-dma) and isopropylamine (15N-ipa) ligands have been prepared and characterised. [1H,15N] HSQC NMR spectroscopy is used to obtain the rate and equilibrium constants for the aquation of cis-[PtCl2(15N-dma)2] at 298 K in 0.1 M NaClO4 and to determine the pKa values of cis-[PtCl(H2O)(15N-dma)2]+ (6.37) and cis-[Pt(H2O)2(15N-dma)2]2+ (pKa1 = 5.17, pKa2 = 6.47). The rate constants for the first and second aquation steps (k1 = (2.12 ± 0.01) × 10−5 s−1, k2 = (8.7 ± 0.7) × 10−6 s−1) and anation steps (k−1 = (6.7 ± 0.8) × 10−3 M−1 s−1, k−2 = 0.043 ± 0.004 M−1 s−1) are very similar to those reported for cisplatin under similar conditions, and a minor difference is that slow formation of the hydroxo-bridged dimer is observed. Aquation studies of cis-[PtCl2(15N-ipa)2] were precluded by the close proximity of the NH proton signal to the 1H2O resonance.

U2 - 10.1016/j.ica.2008.03.117

DO - 10.1016/j.ica.2008.03.117

M3 - Article

VL - 362

SP - 1022

EP - 1026

JO - Inorganica Chemica Acta

JF - Inorganica Chemica Acta

SN - 0020-1693

IS - 3

ER -

Cubo L, Thomas D, Zhang J, Quiroga AG, Navarro-Ranninger C, Berners-Price S. [1H,15N] NMR studies of the aquation of cis-diamine platinum(II) complexes. Inorganica Chimica Acta. 2009;362(3):1022-1026. https://doi.org/10.1016/j.ica.2008.03.117