CHIRAL CHLOROBISMUTHINES STABILIZED BY THE INTRAMOLECULAR COORDINATION OF AN N,N-DIMETHYLAMINO GROUP - X-RAY STRUCTURE-ANALYSIS, ASYMMETRICINDUCTION AT THE BISMUTH CENTER, AND DYNAMIC BEHAVIOR IN SOLUTION

Chiral chlorobismuthines 3 stabilized by intramolecular coordination o f an NN-dimethylamino group have been synthesized by the selective flu orodearylation of the bismuthines 1 with boron trifluoride-diethyl eth er, followed by halogen exchange of the resulting fluorobismuthines 2 with brine. An X-ray crystallographic structure analysis of 3b reveale d that the bismuth centre has a distorted pseudotrigonal bipyramidal s tructure through the formation of a hypervalent 3-centre 4-electron bo nd with the chlorine and nitrogen atoms at apical positions. H-1 NMR s pectra of compounds 3 in CDCl3 at room temperature reflected their fix ed conformation in the solid state. Chiral chlorobismuthines 7a and 7b were obtained in a similar manner starting from optically pure (R)-N, N-dimethyl-1-phenylethylamine as a mixture of two diastereoisomers (77 :23 and 78:22, respectively), the isomeric ratios of which were not in fluenced by the equatorial aryl groups present. Variable-temperature d ynamic H-1 NMR spectra of the diastereoisomeric mixture of 7a provided important information about its behaviour in solution; in [H-2(8)]tol uene dynamic but reversible dissociation of intramolecular Bi-N coordi nation was observed only at elevated temperatures, while in [H-2(6)]-D MSO it occurred quite easily below room temperature, leading to the in version of configuration at the chiral bismuth centre.