| | 1 | Author
| Henri Brunner, Manfred Muschiol, Wilfried Nowak | Requires cookie* | | | Title
| Optisch aktive Übergangsmetall-Komplexe, LVII [1]  | | | | Abstract
| (+)-und (—)-C5H5M(CO)(P02R*)X mit M = Fe, "Fe und X = 1, COCH3, CH3 Optically Active Transition Metal Complexes, LVII [1] (+)-and (—)-C5H5M(CO)(P02R*)X with M = Fe, "Fe, and X = I, COCH3, CH3 In the reaction of C5H5Fe(CO)2l and CsHsFefCO^CHa, respectively, with S-(+)-(C6H5)2PN(CH3)CH(CH3)(C6H5) (abbreviated P02R*) the complexes C5H5Fe(CO)(P02R*)I(l),C5H5Fe(CO)(P02R*)COCH3(2),andC5H5Fe(CO)(P02R !,t)CH3(3) are formed as pairs of diastereoisomers the components of which differ only in the configu-ration at the iron atom. CsH5Fe(CO)(P02R*)CH3 (3) can be obtained in higher yield by photochemical decarbonylation of C5H5Fe(CO)(P02R*)COCH3 (2). The (+)s85-and (—)365-diastereoisomers of each pair exhibit different chemical shifts in the X H NMR spectra. Diastereoisomer separation can be achieved by fractional crystallization. Starting with 57 Fe metal (—)365-C5H5 57 Fe(CO)(P02R*)I was prepared via 57 FeI2, 57 Fe(CO)4l2, C5H5 57 Fe(CO)2l, and C5H5 57 Fe(CO)(P02R*)I in order to demonstrate optical activity of a 57 Fe compound in the y region by Mössbauer polarimetry in later experiments to be reported elsewhere. | | | |
Reference
| Z. Naturforsch. 33b, 407—411 (1978); eingegangen am 24. Januar 1978 | | | |
Published
| 1978 | | | |
Keywords
| Diastereoisomer Separation, X H NMR, Optical Activity, Transition Metal Complexes | | | |
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| default:Reihe_B/33/ZNB-1978-33b-0407.pdf | | | | Identifier
| ZNB-1978-33b-0407 | | | | Volume
| 33 | |
| 2 | Author
| WolfgangA. Herrmann, Ilona Schweizer | Requires cookie* | | | Title
| Übergangsmetall-Methylen-Komplexe, VI [1] Zur irreversiblen -Methylen/Carbonyl-Isomerie zweikerniger Cobalt-Komplexe mit bifunktionellen Methylen-Liganden Transition Metal Methylene Complexes, VI [1] On the Irreversible //-Methylene/Carbonyl Isomerization of Binuclear Cobalt Complexes with Bifunctional Methylene Ligands | | | | Abstract
| Ethyl diazoacetate (2 a) and £erZ-butyl diazoacetate (2 b) are converted into the metal stabilized, doubly bridging alkoxycarbonyl carbenes upon photolysis with (r? 5 -C5H5)Co(CO)2 (1) in tetrahydrofurane at —110°C. Although the yields of //-dicarbonyl-/(-ethoxy-carbonylmethylene-bis(?7 5 -cyclopentadienylcobalt) (3 a) and the corresponding ieri-butyl derivative (3b) are low, both compounds attract considerable attention due to an un-expected and hitherto unknown irreversible carbonyl bridge opening process with concomitant //-methylene rearrangement. These isomerizations have been established by IR and 1 H NMR methods to be first order intramolecular processes. | | | |
Reference
| Z. Naturforsch. 33b, 1128—1135 (1978); eingegangen am 6. Juli 1978 | | | |
Published
| 1978 | | | |
Keywords
| /<-Alkoxycarbonylmethylene, Terminal/Bridging Carbonyl Groups, Cobalt, IR, X H NMR | | | |
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| default:Reihe_B/33/ZNB-1978-33b-1128.pdf | | | | Identifier
| ZNB-1978-33b-1128 | | | | Volume
| 33 | |
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