Catalytic reactions of the type dichloromethane → ketene and chlorobenzene → benzoic acid esters (or benzaldehyde) are possible with Pd complexes, although the turnover numbers are still small. The CCl bond in CH2C12 is even activated by [Pd(PCy3)2(dba)]/PCy3 and the CCl bond in PhCI by Pd(CH3COO)2/PCy3 (Cy = cyclohexyl). The nature of the phosphane is decisive in these reactions : their basicity and cone angle must lie within a certain range. Initial products in the carbonylation are complexes 1 and 2.
075ChemInform Abstract Catalytic carbonylation of the type dichloromethane → ketene, and chlorobenzene → benzoic acid esters or benzaldehyde (the last by presence of alcohols or H2) is possible with Pd complexes such as (III), although the turnover numbers are still small. The C-Cl bond in CH2Cl2 is even activated by (III)/P(cyclohexyl)3 and the C-Cl bond in Ph-Cl by Pd(OAc)2/P(cyclohexyl)3. The nature of the phosphane is decisive in these reactions; their basicity and cone angle must lie in a certain range. The complexes (I), (V) (space group P21/c, Z=4), and (VII) are obtained by equimolar reactions shown. These complexes are initial products in the catalytic carbonylation.
Katalytische Reaktionen vom Typ Dichlormethan → Keten und Chlorbenzol → Benzoesäureester (oder Benzaldehyd) gelingen mit Pd‐Komplexen, wenn auch die Turnover‐Zahlen vorerst noch gering sind. Die C‐Cl‐Bindung in CH2Cl2 wird bereits durch [Pd(PCy3)2(dba)]/PCy3 und die C‐Cl‐Bindung in PhCl durch Pd(CH3COO)2/PCy3 aktiviert (Cy = Cyclohexyl). Entscheidend ist die Natur des Phosphans: Basenstärke und Kegelwinkel müssen in einem bestimmten Bereich liegen. Vorprodukte der Carbonylierung sind die Komplexe 1 und 2.
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