Synthesis, structure, and some reactions of N-(N',N',N'',N''-tetramethyl)guanidinyl-substituted phosphoryl compounds

The tetramethylguanidinyl-substituted phosphoryl compounds 1-10 were prepared in the reaction of the appropriate chlorophosphoryl compounds with either N',N',N '',N ''-tetramethylguanidine (HTMG) or N-trimethylsilyl-(N',N',N '',N ''-tetramethyl)guanidine (TMSTMG). With methyl iodide 1 reacted with N-alkylation to give the ammonium salt 11. 1 reacted with BF3 . Et(2)O at both imino nitrogen atoms with formation of the bis-BF3-adduct 12. The X-ray structure determination of phenylphosphonic acid-bis(N',N',N '',N ''-tetramethylguanidinide) 3 shows shortened PN-bonds and widened PNC-angles, consistent with the partial double bond character of the PN-bond.