Syntheses of P–aryl- and P–alkyl substituted 2,2′,6,6′–tetraphosphanyl–1,1′–biphenyls☆

Add time:09/09/2019    Source:sciencedirect.com

A convenient synthesis of 2,2′,6,6′-tetraphosphanylbiphenyls 1 by lithium/halide exchange and electrophilic reaction with chlorophosphanes or palladium catalyzed phosphanylation is presented. Three examples of 2,2′,6,6′-tetraphosphanylbiphenyls 1b-d were investigated by single crystal X-ray analysis. The coordination behavior of tetraphosphanes 1a,d towards the widely used PdCl2 source Pd(COD)Cl2 (COD = cycloocta-1,5-diene) was investigated by means of NMR spectroscopy. Tetraphosphanes 1a,d form mono (7a,d) as well as dinuclear complexes (2a,d) with the PdCl2 fragment. The coordination of the first PdCl2-fragment to form mononuclear complexes 7a,d can accelerate or moderate the coordination of the second PdCl2-fragment. In case of the crowded tetraphosphane 1a this difference is remarkable and the rate constants for both steps differ by a factor of 50.

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