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. With the corresponding metal salts the anion [N(SPPh2)(SePPh2]−, generated in situ from compound 1 in the presence of KOtBu, readily forms a series of stable bis-chelate complexes [M{N(SPPh2)(SePPh2)}2] (M=Co, 2; Zn, 3; Sn, 4) as well as the tris-chelate complex [Bi{N(SPPh2)(SePPh2)}3] (5). These compounds have been characterized by single-crystal X-ray diffraction and spectroscopic techniques. Compound 1 is isostructural with HN(SPPh2)2 and HN(SePPh2)2 and shows S/Se disorder as do compounds 2–5 where the metal center is coordinated by two or three similar [N(SPPh2)(SePPh2)]− anions. NMR data (δ ppm): 1 — 31P{1H}: 56.9, 52.5 (1JPSe=790 Hz); 77Se{1H}: −160.2 (d, 1JSeP=790 Hz; 2JPP=4.6 Hz). 3 — 31P{1H}: 41.6, 28.2 (1JPSe=525 Hz); 77Se{1H}: −113.1 (d, 1JSeP=524 Hz). 4 — 31P{1H}: 41.7, 28.4 (1JPSe=531 Hz); 77Se{1H}: 14.6 (d, 1JSeP=521 Hz). 5 — 31P{1H}: 38.3, 24.4 (1JPSe=555 Hz); 77Se{1H}: 27.0 (d, 1JSeP=559 Hz).