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Structure of binuclear platinum(III) acetamidate complexes in solutions as probed by 195Pt, 13C,and 1H NMR spectroscopy
Authors:G. A. Kirakosyan  T. N. Fedotova  G. N. Kuznetsova
Affiliation:1.N. S. Kurnakov Institute of General and Inorganic Chemistry,Russian Academy of Sciences,Moscow,Russian Federation;2.A. N. Frumkin Institute of Physical Chemistry and Electrochemistry,Russian Academy of Sciences,Moscow,Russian Federation
Abstract:195Pt, 1H, and 13C NMR spectroscopy was used to study the structure of binuclear platinum(III) acetamidate complexes with 1,10-phenanthroline and 2,2′-bipyridine ligands [Pt2(phen)2(acam)4](NO3)2 (1) and [Pt2(bipy)2(acam)4](NO3)2 (2) in aqueous solutions. The 195Pt NMR spectra of solutions of complexes 1 and 2 in D2O exhibit two signals with satellites due to the 195Pt–195Pt spin-spin coupling (1 J(Pt–Pt) ≈ 6345 Hz), whereas their 1H and 13C NMR spectra contain four sets of signals for the protons and the carbon atoms of the heterocyclic and acetamidate ligands. The signals were assigned using the COSY, NOESY, and HSQC/ HMBC experiments and comparing the coordination shifts of the signals for the protons of heterocycles. These data allowed us to draw a conclusion that binuclear complexes 1 and 2 in solution have a head-to-head structure with nonequivalent platinum(III) atoms (coordination cores PtN5 and PtN3O2), the axial-equatorial coordination of the bidentate heterocyclic molecules, and two bridging and two terminal acetamidate ligands.
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