Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung: XVIII. Darstellung und Charakterisierung von an Kieselgel fixierten Ether-Phosphanen mit Spacern von drei und sechs Kohlenstoffatomen

Abstract

The silylakyl(ether-phosphanes) X n Me 3 n Si(CH 2) m+2 P(Ph)D ( 3a, b, e, 4a, b, e, 5a) [X  Cl, OMe; m = 1, 4; n = 1, 3; D  CH 2C 4H 7O 2 ( 3), CH 2C 4H 7O) ( 4), CH 2CH 2OCH 3 ( 5)] are obtained by a photochemically induced addition of the secondary phosphanes HP(Ph)D to the olefinic double bond of the ω-alkenylchloro-and ω-alkenylmethoxysilanes X n Me 3 n Si(CH 2) m CHCH 2. The corresponding silyalkyl(ether-phosphanes) 3c, d, 4c, d and 5c are obtained from the reaction of the chloropropylmethoxysilanes X n Me 3 n Si(CH 2) m+2 Cl ( 2c,d) with HP(Ph)D in the presence of NaH. The ligands 3a, b, d, e, 4a, b, d, e and 5a can be attached to silica gel. For HCl cleavage lutidine is used as an auxiliary base in the case of the chlorine-containing slylalkyl(ether-phosphanes) 3a, b, 4a, b, 5a. 13C, 29Si, and 31P CP-MAS NMR spectra indicate successful heterogenization, thus giving insight into the nature of the bonding of the ligands with the surface of the silica gel.