Phosphazane Tin Complex
531
toluene at 0◦C. The reaction mixture was warmed up slowly to 25◦C.
After 2 h water ( 0.057 mol) in an H2O-CHCl3 solution was added slowly
to the +mixture. Then the mixture was stirred at 80◦C for another 2 h.
PhNH3 Cl− was filtered off the hot reaction mixture. The solvent was
removed and the white product was washed with cold toluene, then
recrystallized from ethanol (yield 84%), mp 160◦C.
IR (KBr): 3191 (s, NH), 3032–3092 (Ph), 2369 (m, sh, P H), 1175
(P O), 749–690 (CH) cm−1. 1H NMR (25◦C, (CD3)2 SO, ppm): 7.50–6.50
2
1
(m, 10H, Ph), 8.09 (d, JPNH = 8.92 Hz, 2H, NH), and 7.28 (d, JPH
=
596 Hz, 1H, P H). 31P NMR (25◦C, (CD3)2SO, ppm): −4.07 (doublet of
triplet, 1JPH = 612 Hz, 2JPNH = 9.19 Hz).
Synthesis of Bun2 Sn [NPh (O)P(H) NPh (HNEt3)]2 (2)
Bun2SnCl2 (0.130 gr, 0.431 mmol) was dissolved in 10 mL of dry THF,
and added dropwise to a mixture of (C6H5NH)2P(O)H, 1, (0.2 gr, 0.862
mmol) and 1 mL of NEt3 (excess) in 50 mL of dry THF under N2 at
25◦C. Then the mixture was stirred for 48 h. NEt3H+Cl−was filtered
off. The solvent was removed and the pale yellow residue was washed
twice with diethyl ether, hexane and 1 mL of cold THF and dried under
vacuum for 24 h to yield essentially pure 2. (yield 67%), mp 223◦C dec.
IR (KBr): 3438 (broad, NH), 3053 (Ph), 2359 (m, sh, P H), 1093
(P O), 749–683 (Ph), 598 (Sn C), 529 (SnP O), 476 (Sn N) cm−1. MS:
m/z 463, 269, 102, 57, 31.
3
1H NMR (25◦C, (CD3)2SO, ppm): 0.85 (t, JHH = 7.37 Hz, 6H, Bu),
3
3
1.18 (t, JHH = 7.29 Hz, 18H, HNEt3), 1.25 (m, JHH = 7.29 Hz, 4H,
Bu), 1.56 (m, 3JHH = 7 Hz, 4H, Bu), 1.60 (m, 3JHH = 7 Hz, 4H, Bu), 3.04
3
1
(quartet, JHH = 6.64 Hz, 12H, HNEt3), 6.70 (d, JPH = 633 Hz, 2H,
P H), 6.45–7.30 (m, 20H, Ph), 10.28 (s, broad, 2H, HNEt3). 119Sn{ H}
1
NMR (25◦C, (CD3)2SO, ppm): −182 (s). 31P{ H} NMR (25◦C, (CD3)2SO,
1
ppm): 0.87(s, 2JPSn = 125 Hz). 31P NMR: 0.87 (d, 1JPH = 637 Hz).
REFERENCES
[1] R. Keat, The chemistry of Inorganic Homo- and Heterocycles, Vol. II (Academic
Press, London, 1987), pp. 501–589.
[2] R. Keat, Top. Curr. Chem., 102, 89 (1982).
[3] A. D. Norman, Main Group Chem. News, 4, 25 (1996).
[4] L. Stahl, Coord. Chem. Rev., 210, 203 (2000).
[5] G. G. Briand, T. Chivers, and M. Krahn, Coord. Chem. Rev., 233–234, 237 (2002).
[6] T. G. Hill, R. C. Haltiwanger, M. L. Thompson, S. A. Katz, and A. D. Norman, Inorg.
Chem., 33, 1770 (1994).
[7] Z. X. Wang and Y. X. Li, Organometallics, 21, 4641 (2002).