SYNTHESIS AND REACTIVITY OF SAMARIUM COMP LEXES WITH BIS(DIPHENYLCHALCOGENOPHOSPHORYL)AMIDES - THE STRUCTURES OF [(ETA(2)-(PH2PS)(2)N)(2)SM(THF)(2)], (3)-(PH2PSE)(2)N)(ETA(2)-(PH2PSE)(2)N)SM(THF)(2)], [(ETA(3)-(PH2PSE)(2)N)(2)SM(SEPH)(THF)], AND [(ETA(3)-(PH2PSE)(2)N)(2)SM(SEMES)(THF)]

The reaction of potassium-bis(diphenylchalcogenophosphoryl)amides with [SmI2(thf)(5)] affords complexes containing divalent samarium ions. D ifferent structural types were characterised [{eta(2)-(Ph2PS)(2)N}(2)S m(thf)(2)] 1 and a(3)-(Ph2PSe)(2)N}{eta(2)-(Ph2PSe)(2)N}Sm(thf)(2)] 2. The ligands bind either bidentate through the two chalcogen atoms or tridentate through the chalcogen atoms and the nitrogen atom. On oxida tion of 2 with diphenyldiselenide and dimesityldiselenide complexes [{ eta(3)-(Ph2PSe)(2)N}2Sm(SePh)(thf)] 3 or [{eta(3)-(Ph2PSe)(2)N}2Sm(SeM es)(thf)] 4 are formed. (1: Space group Pbca (No. 61), Z = 4, a = 10.7 61(3) Angstrom, b = 17.677(9) Angstrom, c = 29.179(9) Angstrom; 2: Spa ce group P (1) over bar (No. 2), Z = 2, a = 11.152(3) Angstrom, b = 17 .727(9) Angstrom, c = 17.777(6) Angstrom, alpha = 75.33(3)degrees, bet a = 77.74(3)degrees, gamma = 72.21(3)degrees; 3: Space group P2(1)/c ( No. 14), Z = 4, a = 13.399(2) Angstrom, b = 45.868(6) Angstrom, c = 11 .9110(10) Angstrom, beta = 96.889(12)degrees.