Improved synthesis of HN(SPPh2)(SePPh2) and some coordination chemistry of[N(SPPh2)(SePPh2)(-)

The compound HN(SPPh2)(SePPh2) (1) has been synthesized in good yield from the reaction of Ph2P(S)NH2 with Ph2P(Se)Cl in the presence of NaH in THF. W ith the corresponding metal salts the anion [N(SPPh2)(SePPh2](-), generated in situ from compound 1 in the presence of (KOBu)-Bu-t, readily forms a se ries of stable bis-chelate complexes [M{N(SPPh2)(SePPh2)}(2)] (M = Co, 2; Z n, 3; sn, 4) as well as the tris-chelate complex [Bi{N(SPPh2)(sePPh(2))}(3) ] (5). These compounds have been characterized by single-crystal X-ray diff raction and spectroscopic techniques. Compound 1 is isostructural with HN(S PPh2)(2) and HN(SePPh2)(2) and shows S/Se disorder as do compounds 2-5 wher e the metal center is coordinated by two or three similar [N(SPPh2)(SePPh2) ](-) anions. NMR data (delta ppm): 1 - P-31{H-1}: 56.9, 52.5 ((1)J(P-Se) = 790 Hz); Se-77{H-1}: -160.2 (d, (1)J(Se-P) = 790 Hz; (2)J(P-P) = 4.6 Hz). 3 - P-31{H-1}: 41.6, 28.2 ((1)J(P-Se) = 525 Hz); Se-77{H-1}: -113.1 (d, (1)J (Se-P) = 524 Hz). 4 - P-31{H-1}: 41.7, 28.4 ((1)J(P-Se) = 531 Hz); Se-77{H- 1}: 14.6 (d, (1)J(Se-P) = 521 Hz). 5 - P-31{H-1}: 38.3, 24.4 ((1)J(P-Se) = 555 Hz); Se-77{H-1}: 27.0 (d, (1)J(Se-P) = 559 Hz). (C) 2001 Elsevier Scien ce B.V. All rights reserved.