As part of NMR investigations of chemical shifts and couplings of heavy nuclei bonded to each other we have been examining compounds with direct platinu ti nd platinum-lead bonds and now report second-order coupling effects betwee 19 and zo7Pb in platinum-lead compounds. This communication has bee prompted by the recent report (I) of isotopic heteronuclear second-order ~0~~1~~ between ‘17Sn and “‘Sn in (Ru(SnC1,),C1)4and (Os(SnC1,),C1)4-. As an example we take the compound cis-Pt(PPh,),(Ph)(PbPh3) for which the 31P NMR spectrum (2) in dichloromethane consists of two main doublets (6 24.85 ppm, 6 20.80 ppm) arising from the nonequivalent phosphines (2J(31P-3’ Hz). The doublet at higher frequency has satellites (‘J(‘95Pt-31P) = 2 2J(207Pb-31P) = 3460 Hz), which are consistent with a phosphorus tram to and the doublet at lower frequency has couplings (1J(g5Pt-31P) = 1965 Hz, 31P) = 260 Hz), which are consistent with a phosphorus cis to the lead atom. The “*Pt NMR spectrum at 21.3 1 MHz (Fig. 1) of cis-Pt(PPh3),(Ph)(PbFhs) has a central doublet of doublets resulting from coupling to the different phospbor~s atoms and two sets of *“Pb satellites (with the same phosphorus couplings) each f intensity approximately 12% relative to the central multiplet. The two sets of llites are not symmetrically disposed about the central multiplet, their tion being 180 Hz above the frequency of the main multiplet. The *07P spectrum at 20.84 MHz (Fig. 1) is of similar appearance (with different ph uplings) with lg5Pt satellites ( 16% of the central multiplet) unsymmetrically dissed about the central multiplet by 180 Hz to the lower frequency side of the spectrum. Spectra recorded at higher field (lg5Pt at 42.70 MHz, 207Pb at 41.74 MHz) show the asymmetry is decreased to 85 Hz. That the asymmetry is attributable to second-order coupling effects in the satellite spectrum rather than a large isotope effect is endorsed by several experimental observations. The above variation of the asymmetry with frequency is quite the opposite of that expected for an isotope effect, The central multiplets of both spectra have sharp, well-defined lines. In the platinum-195 spectrum this central multiplet corresponds to lg5Pt bonded to lead nuclei with spin 0 (*O’Pb 24%, “‘Pb 52%). gnitude of the asymmetry of the satellites suggests that for a genuine isoto ct the peaks of the central multiplet should be significantly broadened, if split into two multiplets, corresponding to lg5Pt bonded to each of those two nuclei.
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