Synthesis of StableN′,N′,N′′,N′′-Tetramethylguanidine-Substituted σ4(P)- and σ3(P)-Organophosphorus Compounds withN-Protonated P–N Bonds - The First σ3-Phosphorus-Substituted Ammonium Salts⋆

Chalcogeno-urea Ligands on a Phosphadiazonium Lewis Acceptor: A New Synthetic Approach to Ch−P Bonds (Ch = O, S, Se)

“…Calcd for 698.71 g/mol (Found): C 51.6 (51.9), H 7.1 (6.8), N 6.0 (6.0)%. IR: 1597(11), 1413(7), 1393(9), 1364(5), 1265(1), 1221 (6), 1146(4), 1112(8), 1083(13), 1060 (18), 1031(3), 972(14), 927 (19), 904 (17), 884(10),…”

“…Crystals were obtained by liquid-liquid diffusion (see X-ray crystallography), mp 130 °C. IR: 1599 (23), 1554(7), 1497 (6), 1484(9), 1395(12), 1366(8), 1315-(14), 1272(2), 1261(3), 1221(10), 1199(11), 1172 (16), 1153(4), 1114(15), 1098 (22), 1028(5), 1003 (19), 906 (17), 879 (20), 872 (21), 652(13), 637(1), 516 (18). NMR: 1 H 1.3 (s, 9H), 1.5 (s, 18H), 1.6 (d, 3 J HH ) 7 Hz, 12H), 2.3 (s, 6H), 4.6 (septet, 3 J HH ) 7 Hz, 2H), 7.5 (d, 5 J PH ) 1 Hz, 2H); 13 C{ 1 H} 10 (s), 22 (s), 30 (s), 31 (s), 34 (s), 36 (s), 50 (s), 121 (q, 1 J FC ) 319 Hz), 123 (s), 129 (s), 135 (d, 2 J PC ) 39 Hz), 142 (s), 148 (d, 3 J PC ) 10 Hz), 153 (d, 5 J PC ) 1 Hz); 19 F{ 1 H} -78.8 (s, 1 J FC ) 319 Hz); 31 P{ 1 H} 77 (s).…”

“…Calcd for 679.76 g/mol (Found): C 60.1 (58.6), H 6.7 (6.8), N 6.2 (5.8)%. IR: 1673(15), 1600(12), 1563(11), 1495(6), 1405(5), 1300(8), 1280(2), 1247(1), 1224(7), 1174(10), 1157(4); 1129(14), 1109 (16), 1079 (19), 1029(3), 1003- (22), 941 (20), 879 (23), 753 (21), 740 (17), 712(13), 694 (18), 638-(9), 517 (24). Raman: 3067(3), 3007(11), 2964(2), 2929(4), 2907(5), 2879(7), 1600 (6), 1513(1), 1481(9), 1294(13), 1029(12), 1003(8), 123(10).…”

Synthesis and Structures of Complexes Demonstrating the Coordinative Versatility of the 2,4-Diimino-3-phosphinopentene Anion (γ-Phosphino-β-diketiminate)

“…Diketiminate anions ( 1 ) have demonstrated a versatile chelate coordination chemistry with a wide range of metals and some p-block elements. − Complexes of the electron-rich elements of groups 15, , 16, and 17 are notably absent from the series. The extensive coordination chemistry of phosphines as Lewis acceptors − prompted us to examine the possibility of incorporating a phosphenium moiety in the N,N‘ chelate 2 . However, 31 P NMR spectra of reactions between PCl 3 and 3H or 3Li show multiple products.…”

Protonation of phosphoramidites. The effect on nucleophilic displacement

“…3 P-Protonated phosphorous triamide and phosphinous amides have been prepared and characterized, 4 and P()-compounds with tetramethylguanidino groups at phosphorus have been shown to undergo both P-and N-protonation. 5 None of these results, however, justifies any firm conclusions concerning the site of protonation on 1, since the electronic structure of the compounds studied significantly differs from that of 1.…”