Optisch aktive Übergangsmetall-Komplexe, LV [1]. Darstellung und Stereochemie von [C5H5Mo(CO)2 NN’]PF6 mit NN’=Ethylen-diamin und Propylendiamin / Optically Active Transition Metal Complexes, LV [1]. Preparation und Stereochemistry of [C5H5Mo(CO)2NN′]PF6 with NN′=Ethylenediamine and Propylene- diamine

1978 ◽  
Vol 33 (2) ◽  
pp. 247-248 ◽  
Author(s):  
Henri Brunner ◽  
Manfred Muschiol
Keyword(s):  
Nmr Spectroscopy ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Fractional Crystallization ◽  
Optically Active ◽  
H Nmr ◽  
Active Transition

In the reaction of C5H5Mo(CO)3Cl with ethylenediamine and propylenediamine, abbreviated with NN′, the square pyramidal cations [C5H5Mo(CO)2NN′]+ are formed. The diastereoisomeric pairs of enantiomers of the propylenediamine derivative are separated by fractional crystallization. The epimerization at the asymmetric Mo atom (τ1,2 = 30 min, 75 °C, CD3OD solution) can be followed by 1H NMR spectroscopy

scholarly journals Optisch aktive Übergangsmetall-Komplexe, LVII [1] (+)- und (-)-C5H5M(CO)(P∅2R*)X mit M = Fe, 57Fe und X = I, COCH3, CH3 / Optically Active Transition Metal Complexes, L VII [1] (+)- and (-)-C5H5M(CO)(P∅2R*)X with M = Fe, 57Fe, and X = I, COCH3, CH3

1978 ◽  
Vol 33 (4) ◽  
pp. 407-411 ◽  
Author(s):  
Henri Brunner ◽  
Manfred Muschiol ◽  
Wilfried Nowak
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Fractional Crystallization ◽  
Iron Atom ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Optically Active ◽  
H Nmr ◽  
Active Transition

In the reaction of C5H5Fe(CO)2l and C5H5Fe(CO)2CH3, respectively, with S-(+)-(C6H5)2PN(CH3)CH(CH3)(C6H5) (abbreviated P∅2R*) the complexes C5H5Fe(CO)(P∅2R*)I (1), C5H5Fe(CO)(P∅2R*)COCH3 (2), and C5H5Fe(CO)(P∅2R*)CH3 (3) are formed as pairs of diastereoisomers the components of which differ only in the configu­ration at the iron atom. CsH5Fe(CO)(P∅2R*)CH3 (3) can be obtained in higher yield by photochemical decarbonylation of C5H5Fe(CO)(P∅2R*)COCH3 (2). The (+)365- and (-)365-diastereoisomers of each pair exhibit different chemical shifts in the 1H NMR spectra. Diastereoisomer separation can be achieved by fractional crystallization.Starting with 57Fe metal (-)365-C5H557Fe(CO)(P∅2R*)I was prepared via 57Fel2, 57Fe(CO)4l2, C5H557Fe(CO)2l, and C5H557Fe(CO)(P∅2R*)I in order to demonstrate optical activity of a 57Fe compound in the y region by Mössbauer polarimetry in later experiments to be reported elsewhere.

Optisch aktive Übergangsmetall-Komplexe, 84 [1] Substituenten-Effekte in Diastereomerengleichgewichten von quadratisch-pyramidalen Mo-Komplexen / Optically Active Transition Metal Complexes, 84 [1] Substituent Effects in Diastereomer Equilibria of Square-Pyramidal Mo Complexes

1983 ◽  
Vol 38 (7) ◽  
pp. 852-857 ◽  
Author(s):  
Henri Brunner ◽  
Beate Schönhammer
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Nmr Spectra ◽  
Substituent Effects ◽  
Optically Active ◽  
Asymmetric Induction ◽  
Chiral Ligand ◽  
H Nmr ◽  
Active Transition

Amidinato complexes with sub­stituents R at the cyclopentadienyl and R′ in the p-position of the phenyl at the asym­metric C atom were synthesized and characterized. The diastereomers differing in their 1H NMR spectra were partly separated by fractional crystallization. After equilibration with respect to the labile Mo configuration the diastereomer ratio, a measure for the asymmetric induction from the chiral ligand on the formation of the two Mo configura­tions at equilibrium, was determined by 1H NMR integration. The diastereomer ratio decreases for substituents R′ = F and R = CH3, and increases for R' = OCH3, com­pared to the unsubstituted compound.

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