Abstract
AbstractBecause the 195Pt triplet due to coupling with 14N in K[Pt(NH3)Cl3] in D2O is significantly broadened, 1J(195Pt, 14N) determined from the peak separation is not exactly equal to the true coupling constant. It is shown that an accurate value can be determined by a complete lineshape analysis. However, the previously published equation for the lineshape of a spin‐½ nucleus bound to a spin‐1 nucleus is not valid in this case because the intrinsic linewidth of the 195Pt resonance cannot be ignored. A closed expression for the lineshape is given which accounts for the intrinsic linewidth and gives a value for 1J(195Pt, 14N) at 300 K of 235.3±0.2 Hz, in good agreement with the value, 234 Hz, calculated from the published value of 1J(195Pt, 15N) and significantly different than the value, 230.4±1.7 Hz, determined from the peak separation. The T1 of 14N was measured directly by the inversion‐recovery technique and compared with the values extracted from the lineshape. The lineshape T1 values were shown to be unreliable unless T1 ≪ T20, where 1/T20 is the intrinsic linewidth of 195Pt. Also observed was a deuterium isotope effect on the chemical shift of 195Pt of −2.7 ppm per deuteron bound to N and a temperature variation of 0.74 ppm K−1 for the 195Pt chemical shift. Copyright © 2001 John Wiley & Sons, Ltd.
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