Optisch aktive Übergangsmetall-Komplexe, XXVI.

In the reaction of Mn(CO)5Br with the chelating ligand ο-N.N-dimethylaminophenyl diphenyl phosphine (PN) the two enantiomers of fac-Mn(CO)3(PN)Br are formed. Mn(CO)3⁻ (PN)Br interacts with CO/AlCl3 to give the salt [Mn(CO)4(PN)]AlHal4, which can be transformed into [Mn(CO)4(PN)]PF6. The diastereoisomeric compounds Mn(CO)3(PN)COOC10CH19, resulting from the addition of the menthoxide anion to the cation [Mn(CO)4(PN)]+, could not be separated because of their instability. Mn(CO)5Br reacts with the Schiff base NN*, derived from pyridine carbaldehyde(2) and R-α-phenyl ethyl amine, with formation of two isomers of Mn(CO)3(NN*)Br with different configurations at the Mn atom. Both diastereoisomers differ in their 1H NMR spectra and can be obtained in optically active form.

Optisch aktive Übergangsmetall-Komplexe, XXII

Upon irradiation of C5H5V(CO)4 in the presence of the Schiff base, derived from pyridine-carbaldehyde (2) and S-(—)-α-methylbenzyl-amine, two cis CO groups are replaced by the chelating ligand with the formation of complex 3. The reaction of C5H5W(CO)3Cl with 8-hydroxy-quinoline in boiling THF yields the oxinato complex 4. The analogous compound 5 is obtained in the reaction of C5H5Mo(CO)3Cl with 7-carboxy-8-hydroxyquinoline.The new asymmetric complexes with square pyramidal structure are characterised by C, H, N analyses, molecular weight determinations, IR, 1H NMR, UV and mass spectra.