Dakermanji, S. J.; Westendorff, K. S.; Pert, E. K.; Wilson, K. B.; Myers, J. T.; Wilde, J. H.; Dickie, D. A.; Welch, K. D.; Harman, W. D. Spatial Recognition Within Terpenes: Redox and H-bond Promoted Linkage Isomerizations and the Selective Binding of Complex Alkenes. Organometallics 2020, 39, 1961-1975.
Abstract
A method for the resolution of η2-alkene-complex isomers of the type MoTp(NO)(DMAP)(η2-alkene) and WTp(NO)(PMe3)(η2-alkene) (where Tp = hydridotris(pyrazolyl)borate and DMAP = 4-(dimethylamino)pyridine) has been explored. Alkene and polyene compounds form as a mixture of kinetically trapped isomers. For both types of complexes, it was found that addition of either a fluorinated alcohol or one-electron oxidant reduces the number of isomers in solution. Accelerated ligand exchange was also observed, although these reactions were accompanied by significant decomposition.