Abstract
Dialkyl[1,1-bis(alkylchloroalanyl)organylmethyl]phosphine.dialkylchloroalane(1/1) complexes (1a-1d) were synthesized and fully characterized. In 1a-1d, dative bonding between phosphorus or chlorine as a donor atom and aluminum as an acceptor atom results in a bicyclic system. The P-31{H-1} NMR spectra of all compounds dissolved in d(6)-benzene indicate the presence of several isomers in solution. The Al-27{H-1} NMR spectra of 1a-1d dissolved in d(6)-benzene as well show very broad singlets between 177 and 140 ppm. For all compounds, crystal structures consist of two fused four- and five-membered rings. The 1 lambda(3)-phosphaalkyne reacts at the Al-C bond of the starting material, whereas the Al-Cl moiety remains intact. The heterocycle isolated is a molecular complex of the underlying insertion compound and a third equivalent of dialkylaluminum chloride. The four- and five-membered rings both contain two chlorine-bridged aluminum atoms, Al3 and Al1, slightly more symmetrical than that between Al1 and Al6. In the four-membered ring the two aluminum atoms Al1 and Al6 approach each other at an average distance of 289.1 pm which tallies with the element-element distance (286.3pm) in aluminum metal.