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 KO^tBu, 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 (¹J_P-Se = 790 Hz); ⁷⁷Se{¹H}: - 160.2 (d, ¹J_Se-P = 790 Hz; ²J_P-P = 4.6 Hz). 3 - ³¹P{¹H}: 41.6, 28.2 (¹J_P-Se = 525 Hz); ⁷⁷Se{¹H}: -113.1 (d, ¹J_Se-P = 524 Hz). 4 - ³¹P{¹H}: 41.7, 28.4 (¹J_P-Se = 531 Hz); ⁷⁷Se{¹H}: 14.6 (d, ¹J_Se-P = 521 Hz). 5 - ³¹P{¹H}: 38.3, 24.4 (¹J_P-Se = 555 Hz); ⁷⁷Se{¹H}: 27.0 (d, ¹J_Se-P = 559 Hz).