SYNTHESIS AND STRUCTURE OF TETRAORGANOGUANIDINYL-SUBSTITUTED PHOSPHORUS-HALOGEN COMPOUNDS AND OF TRIS-N-(N',N',N'',N''-TETRAMETHYL) GUANIDINYL-PHOSPHONIUM SALTS

The N-(N',N',N'',N''-tetraorgano)guanidine-substituted dichlorophosphi nes 3a - 3c were prepared by the reaction of phosphorus trichloride wi th the corresponding guanidine or N-lithiated guanidine. The high-fiel d shift of the delta(P-31) values of 3a - 3c reflects the strong elect ron-donating effect of the guanidinyl substituents. Attempts to achiev e further substitution of chlorine in PCl3 by N',N',N'',N''-tetramethy lguanidine (HTMG) 1a (employed as such or as its N-trimethylsilyl deri vative, TMSTMG, 2) led to the formation of N-(N',N',N'',N''-tetramethy l)guanidinylphosphonium salts such as 4. A salt containing the same ca tion was obtained from the reaction of N'',N''-tetramethyl)guanidinylt richlorophosphorane 5 with magnesium. N'',N''-tetramethyl)guanidinyltr ichlorophosphorane 6 was obtained from difluorochlorophosphine and HTM G 1a. Hydrolysis of 6 led, depending upon the conditions of the reacti on, either to N',N',N'',N''-tetramethylguanidinium phosphonofluoridate 7 or N-(N',N',N'',N''-tetramethyl)guanidinylphosphonium pentafluoroph osphate 8. A single crystal X-ray structure determination of 8 reveale d a disordered anion and a cation with short P-N bonds, attributed to p pi-p pi interaction. -N-(N',N',N'',N''-tetramethyl)guanidinyl-phosph ine 9 and the N-(N',N',N'',N''-tetramethyl)guanidinyl-phosphines 10 an d 11 were obtained from the corresponding dichlorodiorganoaminophosphi nes and HTMG 1a or rimethylsilyl-(N',N',N'',N''-tetramethyl)guanidine 2.