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Platinum-195 magnetic resonance spectra of some platinum(II) and platinum(IV) complexes

Platinum-195 magnetic resonance spectra of some platinum(II) and platinum(IV) complexes. Pesek, Joseph J.; Mason, W. Roy (Dep. Chem., North. Illinois Univ., DeKalb, Ill., USA). J. Magn. Reson., 25(3), 519-29 (English) 1977. CODEN: JOMRA4. DOCUMENT TYPE: Journal CA Section: 73 (Spectra by Absorption, Emission, Reflection, or Magnetic Resonance, and Other Optical Properties) The 195Pt NMR spectra of 14 sym., substitutionally inert octahedral Pt(IV) and square-planar Pt(II) complexes were measured at 9.75 MHz by using Fourier transform techniques. Chem. shifts obsd. in aq. solns. of the PtL6m complexes cover a range of 6033 ppm and the shielding of the 195Pt nucleus is in the order Cl > 1/2en > Br > SCN > CN > I. For aq. solns. of the PtL4m complexes, the chem. shifts cover a range of 3876 ppm and the order of shielding is Cl > NO2 > NH3 > Br > 1/2en > SCN > CN > I. These results are interpreted in terms of covalency effects in the .sigma. 16920-94-8 and 15321-27-4 are cas registry numbers of chemicals which are used as reagents here.p contribution to shielding. Relaxation times T1 and T2 were measured in several cases where the signal to noise was favorable. The temp. dependence of T1 was investigated for H2PtCl6 and H2PtCl4 in aq. HCl. The relaxation process for these 2 complexes appears consistent with a spin-rotation mechanism. The solvent dependence of the 195Pt resonance in PtCl62- and PtCl42- was also measured for solns. of tetra-n-butylammonium salts in a variety of nonaq. solvents. Some proton and 13C NMR spectra were also obtained for Pt(en)34+ and Pt(en)22+ in aq. soln. and some 13C spectra for Pt(CN)62- and Pt(CN)42- in D2O/H2O. 195Pt spin-coupling consts. were detd. and some of the factors affecting coupling are discussed. .