The phosphorus-31 and metal nuclear magnetic resonance spectra of complexes of tin(II) and lead(II) with tricyclohexylphosphine oxide, sulfide, and selenide

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Abstract
The new stannous and plumbous complexes M(OP(C6H11)3)n2+ (n = 2 or 3, M = Sn or Pb) and [M(SP(C6H11)3)x(SeP-(C6H11)3)3−x]2+ (M = Sn or Pb) have been prepared in SO2 solution and characterized by their reduced temperature slow-exchange 31P and metal (119Sn or 207Pb) nmr spectra. No evidence could be found for complexes in which both OP(C6H11)3 and EP(C6H11)3 (E = S or Se) are coordinated to tin(II) or lead(II). The same pattern of chemical shifts is found in the 119Sn and 207Pb nmr spectra: δM(M(OP(C6H11)3)22+) < δM(M(OP(C6H11)3)32+ < δM(M(SP(C6H11)3)32+) < δM(M(SeP(C6H11)3)32+) and a monotonic but non-linear variation of δM with x for [M(SP(C6H11)3)x(SeP(C6H11)3)3−x]2+. From M(AsF6)2 in SO2 as reference, the range of the metal chemical shifts is 999–2079 ppm and 2407–7707 ppm in the 119Sn and 207Pb nmr spectra respectively. In the 31P nmr spectra, all of the appropriate two-bond M—P couplings are observed, but the fine structure expected from coupling to 31P could not always be observed in those metal nmr spectra which were measured at high field; it is suggested that these metal nmr spectra are "smeared out" by a combination of large temperature sensitivity of the metal chemical shifts and the small temperature variation allowed by the nmr spectrometer temperature controller and/or diffusion along any temperature gradients present along the length of the nmr sample.

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