1H NMR Kinetic Study of Dimethyl Sulfoxide Exchange on Tetrakis(dimethyl- sulfoxide)platinum(II) at Variable Temperature and Pressure: High-pressure NMR kinetics. 36.

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1H NMR Kinetic Study of Dimethyl Sulfoxide Exchange on Tetrakis(dimethyl- sulfoxide)platinum(II) at Variable Temperature and Pressure : High-pressure NMR kinetics. 36. / Ducommun, Yves; Helm, Lothar; Merbach, Andre E.; Hellquist, Björn ; Elding, Lars Ivar.

I: Inorganic Chemistry, Vol. 28, Nr. 2, 01.1989, s. 377-379.

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TY - JOUR

T1 - 1H NMR Kinetic Study of Dimethyl Sulfoxide Exchange on Tetrakis(dimethyl- sulfoxide)platinum(II) at Variable Temperature and Pressure

T2 - High-pressure NMR kinetics. 36.

AU - Ducommun, Yves

AU - Helm, Lothar

AU - Merbach, Andre E.

AU - Hellquist, Björn

AU - Elding, Lars Ivar

N1 - 0020-1669/89/1328-0377

PY - 1989/1

Y1 - 1989/1

N2 - The present report is a 'H NMR investigation of the dimethyl sulfoxide exchange on Pt(Me2S0)42+ as a function of temperature and pressure in CD3N02. Dimethyl sulfoxide is an ambidentate ligand, and the complex contains two 0-bonded and two S-bonded ligands that are exchanging with the free ligand at different rates. It is favorable to follow these exchanges in a non-coordinating diluent like nitromethane, since it allows variation of the ligand concentration, thus giving an opportunity to establish the rate law. The use of a diluent of high dielectric constant and of uncharged ligands minimizes the electrostriction changes along the reaction path, so that the measured volumes of activation will reflect primarily the intrinsic changes of molecular volumes on going to the transition state.

AB - The present report is a 'H NMR investigation of the dimethyl sulfoxide exchange on Pt(Me2S0)42+ as a function of temperature and pressure in CD3N02. Dimethyl sulfoxide is an ambidentate ligand, and the complex contains two 0-bonded and two S-bonded ligands that are exchanging with the free ligand at different rates. It is favorable to follow these exchanges in a non-coordinating diluent like nitromethane, since it allows variation of the ligand concentration, thus giving an opportunity to establish the rate law. The use of a diluent of high dielectric constant and of uncharged ligands minimizes the electrostriction changes along the reaction path, so that the measured volumes of activation will reflect primarily the intrinsic changes of molecular volumes on going to the transition state.

KW - Proton NMR

KW - Dimethyl sulfoxide

KW - Exchange reaction

KW - Platinum(II)

KW - Reaction mechanism

KW - Activation entropy

KW - Activation volume

KW - Fast kinetics

KW - High pressure kinetics

U2 - 10.1021/ic00301a046

DO - 10.1021/ic00301a046

M3 - Article

VL - 28

SP - 377

EP - 379

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 1520-510X

IS - 2

ER -