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Synthesis and Crystal Structure of Bis(tetraphenylphosphonium) Hexabromo-diselenate(II)-bis{dibromodiselenate(I)}, [PPh4]2[Se2Br6(Se2Br2)2], the Salt of a Mixed-valence Bromoselenate(II,I) Anion

Název česky Syntéza a struktura hexabromodiselenatan-bis(dibromodiselenanu) tetrafenylfosfonia [PPh4]2[Se2Br6(Se2Br2)2]
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JANICKIS Vitalijus NECAS Marek

Rok publikování 2008
Druh Článek v odborném periodiku
Časopis / Zdroj Zeitschrift für Anorganische und Allgemeine Chemie
Fakulta / Pracoviště MU

Přírodovědecká fakulta

Citace
www http://dx.doi.org/10.1002/zaac.200700518
Obor Anorganická chemie
Klíčová slova Selenium; Bromoselenates(II-I); Mixed-valence Se(II)-Se(I) compounds; Crystal structure; Tetraphenylphosphonium ion
Popis The Red crystals of [PPh4]2[Se2Br6(Se2Br2)2] (1) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of tetraphenylphosphonium bromide. The crystal structure of 1 has been determined by X-ray diffraction and refined to R = 0.0201 for 4024 reflections. The crystals are triclinic, space group P-1 with Z = 2 and a = 11.2757(4) A, b = 12.3347(5) A, c = 12.4948(5) A, = 113.152(4)deg, = 114.745(4)deg, = 91.208(3)deg (120(2) K). In the solid state the anion of 1 is built up of the Se2Br6 core and two Se2Br2 molecules each of which is linked to one of the trans-positioned terminal Brt atoms of the Se2Br6 core. The central Se2Br6 part consists of a nearly planar arrangement of two planar SeBr4 units sharing a common edge through two 2-bridging Br atoms. The contact between the Brt and the SeI atom of the Se2Br2 molecule is 3.0872(5) A and can be interpreted as a bond of the donor-acceptor type with the Brt as donor and the Se2Br2 molecule as acceptor. The terminal SeII-Br and 2Br-SeII bond lengths are 2.3654(4), 2.6699(5) A and 2.5482(5), 3.0265(5) A, respectively. The bond lengths in the coordinated Se2Br2 molecule are: SeI-SeI = 2.2686(5) A, SeI-Br = 2.3779(5) and 2.3810(5) A.

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