SYNTHESIS, CHIROOPTICAL PROPERTIES AND CATALYTIC ACTIVITY OF DIENE-RHODIUM(I) AND DIENE-IRIDIUM(I) CATIONIC COMPLEXES CONTAINING BINAPHTHYL, C-2-SYMMETRICAL DIAMINE LIGANDS

New cationic rhodium(I) and iridium(I) complexes [M(diene)(diamine)]BF 4 containing chiral C-2-symmetric diamines [M = rhodium; diamine = 2,2 '-diamino-1,1'-binaphthyl (BNDA), diene = cycloocta-1,5-diene (GOD), 1 a, bicyclo[2,2,1]hepta-2,5-diene (NBD), 1b, hexa-1,5-diene (HEX), 1c; diamine = N,N'-dimethyl-2,2'-diamino-1,1'-binaphthyl (DMBNDA), diene = COD, 1d. M = iridium; diamine = BNDA, diene = COD, 2a; diamine = DMBN DA, diene = COD, 2b] have been prepared by the reaction of [MCl(diene) ](2) with AgBF4 and further treatment with the diamine, Using N,N,N',N '-tetramethyl-2,2'-diamino-1,1'-binaphtyl (TMBNDA), no cationic comple x was obtained. With the exception of the complex Ic, complexes 1 and 2 are stable in solution under inert atmosphere. Acetonitrile removes bonded DMBNDA but not BNDA from the metal; KOH removes both the diamin es but not the diene. Complexes 1a, 1b, and 2a, containing (+)(R)-BNDA , catalyze the enantioselective hydrogenation of (Z)-alpha-acetamidoci nnamic acid to acetamidodihydrocinnamic acid (o.p. = 9%; room temperat ure; hydrogen pressure, 35 arm).