Optisch aktive Übergangsmetall-Komplexe, XLIII. (—)578-C5H5Mn(NO)(COC6H5)PN. Darstellung, Epimerisierung und Stereochemie des Ligandenaustauschs

Henri Brunner, Wolfgang Steger
1976 Zeitschrift für Naturforschung. B, A journal of chemical sciences  
In the reaction of [C5H5Mn(NO)(CO)PN*]PF6 (1) with LiC6H5 5-exo-C6H5C5H5Mn(NO)-(CO)PN* (2) and C5H5Mn(NO)(COC6H5)PN* (3) are formed. If the reaction is carried out with optically active starting material 1 the optically active ring addition and benzoyl compounds 2 and 8 resp., are obtained. Whereas the ring addition product 2 is configurationally stable, the benzoyl complex 3 in solution epimerizes according to 1st order kinetics. The change of configuration at the Mn atom occurs by PN*
more » ... tion with formation of a chiral intermediate. This is demonstrated by the fact that exchange of PN* in (-)578-C5H5Mn(NO)(COC6H5)PN* (1a) with P(OC2H5)3 gives (+)578-C5H5Mn(NO)-(COC6H5)P(OC2H5)3 (4a), a reaction proceeding with retention of configuration at the metal atom
doi:10.1515/znb-1976-1113 fatcat:k52gi7xkobf4nfjntgapmcupya