Abstract
The structure of 5-chloromethyl-substituted 1,3,2λ5-diazaphosphorines Cl2P(NCR)2CC(Cl)R'2 (R = H, Cl; R' = Cl, F, CN) and their 1 : 2 solvates with chloroform, and alternative chlorotropy pathways in these compounds with variation of the phosphorus coordination number PIV-PV were studied by semiempirical MNDO-PM3 calculations in the supermolecular approximation. A possibility for isolating metastable PV isomers Cl3P(N = CR)2C = CR'2 containing two imine nitrogen atoms in the equatorial positions of the trigonal bipyramid of phosphorus was demonstrated. The models of limited specific solvation of sigmatropic transition states of P-chlorodiazaphosphorines and related bipolar phosphorus halides were examined. Specific solvation levels out the preferableness of the 1,5-sigmatropic transformation of 5-chloromethyl-1,3,2λ5-diazaphosphorines via unstable intermediate [NC(Cl)R]C = CR'2 over the direct P,C migration of chlorine.
Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
