Structures of [Pd(NH3)2X2] and its chemical transformation in the solid state

Описание

Тип публикации: статья из журнала

Год издания: 2000

Аннотация: Crystal structures of [Pd(NH3)2X2] complexes, where X = Br or I, diamminediiodo-/-dibromopalladium(II), have been studied by X-ray powder diffraction. The series consists of five complexes: cis-[Pd(NH3)2Br2] (I) [a = 13.3202 (7), b = 12.7223 (6), c = 7.05854 (3) A, Z = 8, space group Pbca], trans[Pd(NH3)2Br2] (II) [a = 6.7854 (3), Показать полностьюb = 7.1057 (3), c = 6.6241 (2) A, ? = 103.221 (3), ? = 102.514 (2), ? = 100.386 (3)°, Z = 2, space group P1?], ?-trans-[Pd(NH3)2Br2] (III) [a = 8.4315 (3), b = 8.4206 (3), c = 8.0916 (2) A, Z = 4, space group Pbca], cis-[Pd(NH3)2I2] (IV) [a = 13.9060 (8), b = 13.5035 (8), c = 7.5050 (4) A, Z = 8, space group Pbca], and ?-trans-[Pd(NH3)2I2] (V) [a = 8.8347 (5), b = 8.8410 (5), c = 8.6081 (2) A, Z = 4, space group Pbca]. Patterson synthesis and Rietveld refinement have been used for structural determination. Molecular structures with column-or parquet-type packing of flat complexes are characteristic of these substances. Corresponding cis- and ?-trans compounds are isostructural. The thermal transformations cis>trans>?-trans (cis>?-trans in the case of iodine) are considered. Cl derivatives are also discussed. The transformations proceed irreversibly and are accompanied by decreasing specific volume. Owing to these features, they can be classified as chemical reactions. High-temperature X-ray powder diffraction was used to study the transformations in air. The set of data is consistent with a solid state transformation from cis to trans. According to this model, the columns of molecules remain intact during the process, and the transformation proceeds via the breaking of Pd?X and Pd?N intermolecular bonds. The powder diffraction data have been deposited in ICDD-JCPDS (45-0596, 46-0876, 46-0879, 47-1690, 48-1185).

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Издание

Журнал: Acta Crystallographica Section B: Structural Science

Выпуск журнала: Vol. 56, Is. 3

Номера страниц: 419-425

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