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note
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31P sites. This is consistent with the allyl rocking proposal (9 ⇀ 9′). If two conformations of the tricyclohexylphosphine ligand were possible, then three isomers would be expected for 9. Only one isomer of the three would exhibit inequivalent phosphorus nuclei. It seems unlikely that this would be the sole isomer detectable. Thus we favor allyl rocking to account for the dynamics of 9 and, by analogy, for the dynamics of the other allyl complexes.
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8944234751
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There is no evidence that this species is a bis-ethy!ene complex. However, since ethylene readily displaces diethyl ether in these cationic species, we believe a bis-ethylene complex is more likely than a solvated mono-ethylene complex.
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8944254600
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We cannot rule out the presence of both 16 and 16′ in rapid equilibrium at 25 °C. Associative exchange of bound and free acrylate is rapid on the NMR time scale at 25 °C (see above); the five coordinate intermediate responsible for associative exchange thus could provide a mechanism for very rapid interconversion of 16 and 16′.
-
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54
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8944225402
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note
-
The NMR analysis of the sequence 19 → 20 → 21 is more complicated than the analogous transformations for the tricyclohexyl phosphine complexes 13 → 14 → 16. The rate of 19 → 20 is only slightly faster than the 20 → 21 conversion and thus 20 never appears without substantial amounts of either 19 and/or 21 present.
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