Diaminehalogenoplatinum(II) complex reactions with DMSO

作者：Josephsen Jens^*

来源：Inorganica Chimica Acta, 2018, 478: 54-58.

DOI：10.1016/j.ica.2018.03.039

• Platinum(II) diamine complexes
• Substitution reaction rates
• DMSO

The platinum(II) complexes [Pt(N-N)X-2] (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 [PtenCl(2)] 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 [PtenI(2)] 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) X-2] 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.

• 出版日期2018-6-1