Studien zum Vorgang der Wasserstoffübertragung, 70 [1] Über den Einfluß der Struktur des Co-Katalysators auf die Hydrierung von Hexen-1 mit Rh(I)-Phosphin-Komplexen. Gibt es einen „Scheibenwischer-Effekt“?/Studies on the Occurrence of Hydrogentransfer, 70 [1] On the Influence of the Structure of the Co-Catalyst upon the Hydrogenation of Hexene-1 with Rh(I)-Phosphine-Complexes. Exists a Wind-Screen-Wiper-Effect?

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Abstract
It is well known, that OMe and NMe2 - substituents in the ortho-position of phenyl groups linked to phosphorus as a center o f chirality induce a high optical activity to derivatives of α-acylaminoacrylic acid in the homogeneous hydrogenation with Rh(I)-Phosphine complexes. The influence of the number, position and the nature of OR-substituents in the aromatic systems of tertiary phosphines upon the rate of the hydrogentransfer to hexene-1 as olefine is investigated and discussed (Tables I to V ). For an explanation of the chemical behaviour of co-catalyst containing o-RO-phenylsubstituents a short lasting coordinative interaction between the oxigen atom of the OR-substituent and the Rh(I) as the central atom is postulated (wind-screen-wipereffect), which stabilizes the configuration of a catalytic active intermediate. Triarylarsines with o-RO-phenyl substituents have a lower catalytic activity, as the corresponding phosphines as co-catalysts (Tables VI to VIII).

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