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The Hydrolysis Kinetics of ds-diamminedichloroplatinum(II). 10. Activation Volumes for Halide Anation of Some czs-[Pt(N)2(OH2)2]2+ Systems by Kathryn Hindmarsh; Donald A. House; Rudi van Eldik is a Chemistry article available to read on EtoBox.

What is The Hydrolysis Kinetics of ds-diamminedichloroplatinum(II). 10. Activation Volumes for Halide Anation of Some czs-[Pt(N)2(OH2)2]2+ Systems about?

For the following equations relating to the aquation and anation processes of cisplatin and similar squareplanar platinum(II) diamine complexes: [PtX2(N)2] + H20 k [PtX(N)2(OH2)] + + Χ" (1) k-, [PtX(N)2(OH2)] + + H20 % [Pt(N)2(OH2)2] 2+ + X" k-2 (2) rate constant (k 2, Μ 1 s \ 25° C), activation enthalpy (ΔΗ\*, kj mol 1 ), activation entropy (AS\*, J Κ 1 mol 1 ) and activation volume (AV\*, cm 3 mol ) data have been found for the bromide anation of cis-[Pt(N)2(OH2)2] 2+ where (N)2 = tn, en, ds^NHj)^ irans-(NH3)2, Me2tn, chxn; CJS-(NH3)2: fc\_2 = 0.45, AH\* = 68, AS\* = -25, ir«ns-(NH3)2:4.23,56, -44, chxn: 1.13, 70, -9, Me2tn: 1.53, 65, -24, en: 1.29, 71, -5, ΔV\* = -5.3, tn: 1.86,68, -12, Δ V\* = -7.4. Further activation volumes (AV\*, cm 3 mol have been determined for selected k 1 and fc\_ 2 bromide or chloride anation data. L,(cm 3 mol -1 , CI -): en -7.4. k\_i(cm 3 mol \ Br"): ci's-(NH3)2 -11, en -9.4, tn -7.66. fc\_2(cm 3 mol -1 , CI -): cis-(NH3)2 -5.1, en -5.7, tn -5.8. For all kx above where A V\* has been measured, values lie in the range -4 to -11 cm 3 mol 1 and apart from two exceptions AS\* is negative in 36 cases implying an associative mechanism for the substitution p

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Author

Kathryn Hindmarsh; Donald A. House; Rudi van Eldik

Publisher

Walter de Gruyter GmbH

Published

1999

Language

EN

Field

Chemistry (Physical Sciences)