Diaminehalogenoplatinum(II) complex reactions with DMSO

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Resumé

The platinum(II) complexes [Pt(N-N)X2] (X = Cl, Br, and I; (N-N) = 1,2-ethanediamine (en) and 1,3-propanediamine (tn)) have been synthesised; their reactions with DMSO in DMSO to substitute halogenide were followed using changing integrals of NMR-spectroscopic signals. The rate constant for [PtenCl2] was found to be 1.0*10−4 s−1 at 300 K and from kinetic runs at different temperatures the energy of activation was estimated as 82 kJ*mol−1 in this case.

The rate constant depends on the size of halogenide and was found to be forty times larger for [PtenI2] than for its dichloro-analogue. In the tn-series reactions were a little faster than in the en-series.

For all six [Pt(N-N)X2] complexes the solvolysis stopped at the coordination of one DMSO and the six new [Pt(N-N)DMSOX]X were isolated and characterised. Further the [PtenDMSOCl]+ was isolated as its nitrate and perchlorate. DMSO exchange reactions (in DMSO) of [PtenDMSOX]+ were found to be slightly slower than the solvolysis reactions, iodide again giving rise to the most labile system.

Ion pair formation in DMSO was found to be modest to almost negligible with a formation constant of 30 M−1 in the case of [PtenDMSOCl]Cl as the largest.
OriginalsprogEngelsk
TidsskriftInorganica Chimica Acta
Vol/bind478
Sider (fra-til)54-58
Antal sider5
ISSN0020-1693
DOI
StatusUdgivet - 28 mar. 2018

Citer dette

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title = "Diaminehalogenoplatinum(II) complex reactions with DMSO",
abstract = "The platinum(II) complexes [Pt(N-N)X2] (X = Cl, Br, and I; (N-N) = 1,2-ethanediamine (en) and 1,3-propanediamine (tn)) have been synthesised; their reactions with DMSO in DMSO to substitute halogenide were followed using changing integrals of NMR-spectroscopic signals. The rate constant for [PtenCl2] was found to be 1.0*10−4 s−1 at 300 K and from kinetic runs at different temperatures the energy of activation was estimated as 82 kJ*mol−1 in this case.The rate constant depends on the size of halogenide and was found to be forty times larger for [PtenI2] than for its dichloro-analogue. In the tn-series reactions were a little faster than in the en-series.For all six [Pt(N-N)X2] complexes the solvolysis stopped at the coordination of one DMSO and the six new [Pt(N-N)DMSOX]X were isolated and characterised. Further the [PtenDMSOCl]+ was isolated as its nitrate and perchlorate. DMSO exchange reactions (in DMSO) of [PtenDMSOX]+ were found to be slightly slower than the solvolysis reactions, iodide again giving rise to the most labile system.Ion pair formation in DMSO was found to be modest to almost negligible with a formation constant of 30 M−1 in the case of [PtenDMSOCl]Cl as the largest.",
author = "Jens Josephsen",
year = "2018",
month = "3",
day = "28",
doi = "10.1016/j.ica.2018.03.039",
language = "English",
volume = "478",
pages = "54--58",
journal = "Inorganica Chimica Acta",
issn = "0020-1693",
publisher = "Elsevier BV",

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Diaminehalogenoplatinum(II) complex reactions with DMSO. / Josephsen, Jens.

I: Inorganica Chimica Acta, Bind 478, 28.03.2018, s. 54-58.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Diaminehalogenoplatinum(II) complex reactions with DMSO

AU - Josephsen, Jens

PY - 2018/3/28

Y1 - 2018/3/28

N2 - The platinum(II) complexes [Pt(N-N)X2] (X = Cl, Br, and I; (N-N) = 1,2-ethanediamine (en) and 1,3-propanediamine (tn)) have been synthesised; their reactions with DMSO in DMSO to substitute halogenide were followed using changing integrals of NMR-spectroscopic signals. The rate constant for [PtenCl2] was found to be 1.0*10−4 s−1 at 300 K and from kinetic runs at different temperatures the energy of activation was estimated as 82 kJ*mol−1 in this case.The rate constant depends on the size of halogenide and was found to be forty times larger for [PtenI2] than for its dichloro-analogue. In the tn-series reactions were a little faster than in the en-series.For all six [Pt(N-N)X2] complexes the solvolysis stopped at the coordination of one DMSO and the six new [Pt(N-N)DMSOX]X were isolated and characterised. Further the [PtenDMSOCl]+ was isolated as its nitrate and perchlorate. DMSO exchange reactions (in DMSO) of [PtenDMSOX]+ were found to be slightly slower than the solvolysis reactions, iodide again giving rise to the most labile system.Ion pair formation in DMSO was found to be modest to almost negligible with a formation constant of 30 M−1 in the case of [PtenDMSOCl]Cl as the largest.

AB - The platinum(II) complexes [Pt(N-N)X2] (X = Cl, Br, and I; (N-N) = 1,2-ethanediamine (en) and 1,3-propanediamine (tn)) have been synthesised; their reactions with DMSO in DMSO to substitute halogenide were followed using changing integrals of NMR-spectroscopic signals. The rate constant for [PtenCl2] was found to be 1.0*10−4 s−1 at 300 K and from kinetic runs at different temperatures the energy of activation was estimated as 82 kJ*mol−1 in this case.The rate constant depends on the size of halogenide and was found to be forty times larger for [PtenI2] than for its dichloro-analogue. In the tn-series reactions were a little faster than in the en-series.For all six [Pt(N-N)X2] complexes the solvolysis stopped at the coordination of one DMSO and the six new [Pt(N-N)DMSOX]X were isolated and characterised. Further the [PtenDMSOCl]+ was isolated as its nitrate and perchlorate. DMSO exchange reactions (in DMSO) of [PtenDMSOX]+ were found to be slightly slower than the solvolysis reactions, iodide again giving rise to the most labile system.Ion pair formation in DMSO was found to be modest to almost negligible with a formation constant of 30 M−1 in the case of [PtenDMSOCl]Cl as the largest.

U2 - 10.1016/j.ica.2018.03.039

DO - 10.1016/j.ica.2018.03.039

M3 - Journal article

VL - 478

SP - 54

EP - 58

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

ER -