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Spatial Recognition Within Terpenes: Redox and H‑bond Promoted Linkage Isomerizations and the Selective Binding of Complex Alkenes

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journal contribution
posted on 27.04.2020, 19:44 authored by Steven J. Dakermanji, Karl S. Westendorff, Emmit K. Pert, Katy B. Wilson, Jeffery T. Myers, Justin H. Wilde, Diane A. Dickie, Kevin D. Welch, W. Dean Harman
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.