Abstract
Complex formation between PCl5 and a variety of pyridine bases has been investigated in solution by means of 31P n.m.r. spectroscopy. Most unidentate pyridines form molecular 1 : 1 adducts co-ordinated via the pyridine nitrogen, although 2-cyanopyridine may be attached via the cyano-group. Complex formation appears to be inhibited by both steric and electronic effects, but steric hindrance seems to be more important. Some methyl-substituted pyridines are chlorinated by PCl5, with formation of PC3. Bidentate pyridines form ionic derivatives [PCl4L][PCl6](2 : 1), [PCl4L]Cl (1 : 1), or mixtures of these, but the stable species in concentrated solution is the 2 :1 adduct. Some of the adducts have been isolared and characterised by a number of physical techniques. The solid-state structures appear to correspond with those in solution, except for derivatives of bidentate pyridines mentioned above.
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