92% |
In acetonitrile;Reflux; |
Solid AgSCN (0.0534g, 0.322mmol) was added to a solution of 4-dimethylaminophenyl-diphenyl phosphine (0.1967g, 0.644mmol) in acetonitrile (100cm3). The reaction was heated under reflux overnight in order to dissolve all solids. The solution was filtered while hot and it was allowed to crystallise from which white cubic crystals were isolated (0.2302 g, 92percent). Anal. Calcd for C41H40AgN3SP2: C, 63.40; H, 5.19; N, 5.41; S, 4.13. Found: C, 63.39; H, 5.56; N, 5.42; S, 3.78. Solid IR (nu in cm?1): 3067, 3045 (nu (=C?H),w); 2888, 2852 (nu (alkane, delta (C?H), asymm, w) 2361 (w); 2074 (nu (SCN), m); 1596, 1545, 1510, 1479, 1431 (nu (C=C aromatic), m); 1360, 1307, 1291 (nu (delta (CH3), m); 1229, 1202, 1183, 1156 (nu (N?CH3, m), dimethyl amino, w); 1102 (nu (P?C), s); 1060 (nu (C?N), dimethyl amino, s); 999, 945, 917 (nu (delta (=C?H), m); 808; 743, 695, 610 (nu, delta (=C?H), s). 1H NMR (400MHZ, d6-DMSO): delta(ppm) 2.914 (CH3); 6.635 (d, 3J(Ha,b-H)=8.4Hz, Ha, Hb, 4-dimethylamino phenyl); 7.180 (t, 1J=9.6Hz, phenyl p-H); 7.266 (t, 1J=8.8Hz, H-aromatic, phenyl); 7.338 (t, 1J=7.4Hz, phenyl m-H); 7.426 (t, 1J=7.2Hz, phenyl H). 13C{H} NMR (100MHz, d6-DMSO): delta (ppm) 112.010 (d, 2J(P?C)=10.6Hz, meta C, 4-dimethylamino phenyl); 128.727 (d, 3J(P?C)=8.8Hz, meta C, phenyl); 129.859 (para C, phenyl); 132.939 (d, delta1=133.018, delta2=132.860, 2J(P?C)=15.8Hz, meta 4-dimethylamino phenyl); 133.539 (d, 1J(P?C)=25.2Hz, ipso C, phenyl); 135.21 (d, 2J(P?C)=18.5Hz, ortho C, 4-dimethylamino phenyl); 151.49 (para C, 4-dimethylamino phenyl). 31P{H} NMR (161MHz, d6-DMSO): delta (ppm) 6.27. 1H NMR (400MHZ, CDCl3): delta(ppm) 3.137 (CH3); 7.334 (m, H-aromatic, phenyl); 7.405 (m, H-aromatic, phenyl); 7.466 (m, H-aromatic, phenyl); 7.223 (m, H-aromatic, phenyl). 13C{H} NMR (100MHz, CDCl3): delta (ppm) 40.01 (CH3); 112.325 (d, 3J(P?C)=11.0Hz, meta C, 4-dimethylamino phenyl); 128.706 (d, 3J(P?C)=9.4Hz, meta C, phenyl); 129.688 (para C, phenyl); 133.446 (d, 2J(P?C)=15.8Hz, ortho C, 4-dimethylamino phenyl); 135.680 (d, 2J(P?C)=18.1Hz, ortho C, 4-dimethylamino phenyl); 151.66 (para C, 4-dimethylamino phenyl). 31P{H} NMR (161MHz, CDCl3): delta (ppm) 7.83. |