ISSN:
0044-2313
Keywords:
Samarium complexes
;
crystal structure
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Synthesis and Reactivity of Samarium Complexes with Bis(diphenylchalcogenophosphoryl)amides. The Structures of [{η2-(Ph2PS)2N}2Sm(thf)2],[{η3-(Ph2PSe)2N}{η2-(Ph2PSe)2N}Sm(thf)2],[{η3-(Ph2PSe)2N}2Sm(SePh)(thf)], and [{η3-(Ph2PSe)2N}2Sm(SeMes)(thf)]The reaction of potassium-bis(diphenylchalcogenophosphoryl)amides with [SmI2(thf)5] affords complexes containing divalent samarium ions. Different structural types were characterised [{η2-(Ph2PS)2N}2Sm(thf)2] 1 and [{η3-(Ph2PSe)2N}{η2-(Ph2PSe) 2N}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 oxidation of 2 with diphenyldiselenide and dimesityldiselenide complexes [{η3-(Ph2PSe)2N}2Sm(SePh)(thf)] 3 or [{η3-(Ph2PSe)2N}2Sm(SeMes)(thf)] 4 are formed.(1: Space group Pbca (No. 61), Z = 4, a = 10.761(3) Å, b = 17.677(9) Å, c = 29.179(9) Å;2: Space group P1 (No. 2), Z = 2, a = 11.152(3) Å, b = 17.727(9) Å, c = 17.777(6) Å, α = 75.33(3)°, β = 77.74(3)°, γ = 72.21(3)°;3: Space group P21/c (No. 14), Z = 4, a = 13.399(2) Å, b = 45.868(6) Å, c = 11.9110(10) Å, β = 106.422(10)°;4: Space group P21/n (No. 14), Z = 4, a = 12.034(2) Å, b = 36.533(3) Å, c = 14.6617(10) Å, β = 96.889(12)°)
Notes:
Durch Umsetzungen von Kalium-Bis(diphenylchalkogenophosphoryl)amid mit [SmI2(thf)5] bilden sich Komplexe mit zweiwertigen Samariumionen. Es werden verschiedene Strukturtypen charakterisiert: [{η2-(Ph2PS)2N}2Sm(thf)2] 1 bzw. [{η3-(Ph2PSe)2N}{η2-(Ph2PSe) 2N}Sm(thf)2] 2. Der Ligand bindet entweder zweizähnig über die beiden Chalkogenatome oder dreizähnig über die Chalkogenatome und das Stickstoffatom. Wird 2 mit Diphenyldiselenid oder Dimesityldiselenid oxidiert, bilden sich die Komplexe [{η3-(Ph2PSe)2N}2Sm(SePh)(thf)] 3 bzw. [{η3-(Ph2PSe)2N}2Sm(SeMes)(thf)] 4.(1: Raumgruppe Pbca, (Nr.61), Z = 4, a = 10,761(3) Å, b = 17,677(9) Å, c = 29,179(9) Å;2: Raumgruppe P1 (Nr.2), Z = 2, a = 11,152(3) Å, b = 17,727(9) Å, c = 17,777(6) Å, α = 75,33(3)°, β = 77,74(3)°, γ = 72,21(3)°;3: Raumgruppe P21/c (Nr. 14), Z = 4, a = 13,399(2) Å, b = 45,868(6) Å, c = 11,9110(10) Å, β = 106,422(10)°;4: Raumgruppe P21/n (Nr. 14), Z = 4, a = 12,034(2) Å, b = 36,533(3) Å, c = 14,6617(10) Å, β = 96,889(12)°)
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.199762301119
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