title: Diastereoselective proton transfer: a route to enantiomerically pure half-sandwich rhenium complexes.
abstract: The diastereomeric methyl rhenium complex [CpRe(NO){P(Me)(Ph)(2-C6H4NMe2)}(CH3)] was prepared in two steps from chiral racemic [CpRe(NO)(CO)(NCMe)]BF4 and the chiral racemic phosphine P(Me)(Ph)(2-C6H4NMe2). The unlike diastereomer reacts preferentially with MeSO3H to give the ring-closed ionic complex unlike-[CpRe(NO){P(Me)(Ph)(2-C6H4NMe2)}]MeSO3 along with unreacted like-[CpRe(NO){P(Me)(Ph)(2-C6H4NMe2)}(CH3)], which is easily separated and converted to like-[CpRe(NO){P(Me)(Ph)(2-C6H4NMe2)}]MeSO3. Starting from (R)-P(Me)(Ph)(2-C6H4NMe2), the diastereomerically and enantiomerically pure complexes (RRe,SP)-[CpRe(NO){P(Me)(Ph)(2-C6H4NMe2)}]MeSO3 and (SRe,SP)-[CpRe(NO){P(Me)(Ph)(2-C6H4NMe2)}]MeSO3 were obtained. Thus, this reaction sequence demonstrates a highly diastereoselective proton transfer from a functionalized chiral phosphine to a transition metal. Furthermore, it provides efficient access to enantiomerically pure half-sandwich rhenium complexes.
authors.affiliation: Institut für Anorganische Chemie, Bayerische Julius-Maximilians-Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany.
authors.forename: Frank
authors.initials: F
authors.lastname: Bock
authors.forename: Frank
authors.initials: F
authors.lastname: Fischer
authors.forename: Wolfdieter A
authors.initials: WA
authors.lastname: Schenk