Synthesis, Characterization, and Solution Properties of Skeletally Stabilized Triphosphazanes

Abstract

The new skeletally stabilized dichlorotriphosphazanes C6H4N2(PhPCl)2PPh (5) and C6H4N2(MePCl)2PMe (6) have been prepared from reactions between PhPCl2 or MePCl2 and 1,2-(NH2)2C6H4 or 1,2-(Me3SiNH)2C6H4, respectively. Reaction of PhPCl2 with the phosphadiazole C2H4(Me3SiN)2PPh yields triphosphazane C2H4N2(PhPCl)2PPh (8). Compounds 5, 6, and 8 form as mixtures of three diastereomers; characterization is based on spectral data and derivatization of 5 and 8 to the amino and thio(amino) triphosphazanes C6H4N2[PhP(NHiPr)]2PPh (7) and C2H4N2[PhP(S)NEt2]2PPh (10). The 31P NMR spectra of 5 and 6 in solution have been measured as a function of temperature and solvent donor and dielectric strength. The solution properties of the dichlorotriphosphazanes and the implications of these on subsequent reaction chemistry are discussed.

Gallium Halide Induced Heterocycle Expansion of Dihalodiphosphadiaryldiazanes [(XPNR)2] to the Corresponding Triphosphatriazanes [(XPNR)3]

“…4,5 Few examples of halophosphazane trimers 3 have been reported, [6][7][8] and in general, cyclic (R′PNR) n oligomers with n > 2 are rare. [8][9][10][11][12] Extended cyclic phosphazanes are only observed with "skeletal stabilization" [11][12][13][14][15][16][17][18][19] or tethering of cyclodiphos- phadiazane units. [20][21][22][23][24][25][26][27] Preference for the diphosphadiazane framework contrasts the wide range of oligomeric arrangements that are well-known for phosphorus(V)-nitrogen compounds (phosphazenes) usually represented by 3(V) 28 (isomeric with 3, disregarding exocyclic substituents), while dimeric phosphazenes 2(V) are very rare.…”

“…615 (20), 740 (13), 775(3), 895(1), 920(4), 976 (14), 983 (15), 1032 (16), 1074 (17), 1097 (9), 1167 (11), 1209(2), 1262 (8), 1283 (10) 31 P{ 1 H} (CDCl 3 ), 231; 1 H (CDCl 3 ), 2.74 (s), 7.13 (s). IR: 410 (8), 440(1), 496(4), 530(5), 559 (13), 586 (17), 670 (20), 740 (15), 770(2), 889(3), 920 (7), 977 (14), 1033 (16), 1099 (10), 1167 (11), 1207 (6), 1247 (19), 1261 (9), 1287 (12), 1581 (18). a Two essentially indistinguishable molecules in the asymmetric unit, parameters given for one molecule.…”

“…31 P{ 1 H} NMR (CH 2 Cl 2 ): 193 K, 87 (s), 208 (broad singlet); 298 K, 268 (s). IR: 401 (12), 427 (15), 466 (20), 472 (16), 488 (11), 801(5), 803(4), 849 (17), 856 (18), 932 (19), 962 (2), 970(3), 977 (1), 1006 (13),1041 (14), 1095 (7), 1152 (10), 1364 (9), 1384 (8), 1436 (6).…”

N-{Bis[methyl(phenyl)amino]phosphoryl}-2,2,2-trichloroacetamide

“…For background to the chemistry of phosphorus-containing systems, see: Helm et al (1999); Katti et al (1991). For the biological and pharmacological properties of carbacylamidophosphate derivatives, see: Jaroslav & Swetdloff (1985).…”

“…The intensive development of the chemistry of the phosphorus containing systems during the last decades has given rise to synthesis of many compounds bonded by phosphorus and nitrogen atoms (Helm et al, 1999;Katti et al, 1991).…”