Solid State Structures of AsCl5 and SbCl5

Abstract

Arsenic pentachloride has a trigonal bipyramidal structure in the solid state with As-Cl eq ϭ 210.6,211.9 pm, As-Cl ax ϭ 220.7 pm, space group Pmmn, a ϭ 706.2 (1); b ϭ 760.3 (2), c ϭ 623.3 (1) pm. Antimony pentachloride exists in two modifications: above Ϫ 54.1°C it is also trigonal bipyramidal with Sb-Cl eq ϭ 227.0 and Sb-Cl ax ϭ 233.3 pm, space group P6 3 /mmc, a ϭ 741.4 (1), c ϭ 799.0(2)pm. Below Ϫ54.1°C it changes reversibly into a double chlorine bridged dimer resulting in an edge shared double octahedral structure, space group P2 1 /c, a ϭ 952.4 (1), b ϭ 1189.9 (1), c ϭ 1219.7 (1) pm, β ϭ108,27 (1): In presence of water the formation of AsCl 5 is hindered, two salts containing the octahedral anion Die Festkörperstrukturen von AsCl 5 und von SbCl 5Inhaltsübersicht. Arsenpentachlorid ist im festen Zustand trigonalbipyramidal aufgebaut, As-Cl eq ϭ 210.6, 211.9 pm und As-Cl ax ϭ 220.7 pm, Raumgruppe Pmmn, a ϭ 706.2 (1), b ϭ 760.3 (2), c ϭ 623.3 (1) pm. Antimonpentachlorid kommt in zwei Modifikationen vor: oberhalb Ϫ54.1°C ist es ebenfalls trigonal-bipyramidal aufgebaut, Sb-Cl äq ϭ 227.0 und Sb-Cl ax 233.3 pm, Raumgruppe P6 3 /mmc, a ϭ 741.4 (1), c ϭ 794.0 (2) pm. Unterhalb Ϫ 54.1°C lagert es sich reversibel um in ein doppelt chlorverbrücktes Dimer mit einer kantenverknüpften doppeloktahedrischen Struktur, Raumgruppe P2 1 /c, aϭ 952.4 (1), b ϭ 1189.9 (1), c ϭ 1219.7 (1)

Enhanced luminescence properties through heavy ancillary ligands in [Pt(C^N^C)(L)] complexes, L = AsPh3 and SbPh3

“…We assume that the observed deviations from the linear trend (especially for k nr ) are due to 3d-contraction anomaly related to the first filling of a d-shell before the element As. 77,78 At 298 K, k r for the dba complexes also increases from P to Sb, but no clear trend can be deduced from the k nr values, which we attribute to more complex rotovibronic relaxation pathways between T 1 and S 0 or possibly via the population of dissociative 3 MC states at ambient temperature (Fig. 5C).…”

The crystal structure of a new mixed valence arsenic(III,V)oxoacid H6As3+ 7As5+ 7O31

“…5b) with bond lengths for As(2)--O varying from 1.67 A to 2.02 A and an average bond length of about 1.82 A. Up to now, pentavalent arsenic with coordination number 5 was only known for the As 5þ X 5 halides with X ¼ F, Cl [22,23] having the geometry of a trigonal bipyramid, while with oxygen atoms as ligands only As 5þ O 4 tetrahedra and As 5þ O 6 octahedra are known so far. The As 5þ O 5 square pyramids are interconnected in a zigzag manner along c-axis by As (2) The second polyhedron is the typical trigonal pyramid As 3þ O 3 for trivalent arsenic [24,25] as it is exhibited by As(1) (Fig.…”

Synthesis of bis-spiro piperidines using nano γ-alumina supported Sb(v) under ultrasonic irradiation at room temperature conditions

“…26,27 Among the three used elements (As, Sb or Bi), only As and Sb form with chloride preclude any coordination chemistry with ligands. 28 SbCl 5 is a powerful Lewis acid and a strong chlorinating agent, widely used in organic synthesis, and a large number of complexes with O-or N-donor solvents have been reported. 29,30 The handling and the usability of SbCl 5 in liquid form is laborious and the supported form is indeed preferable.…”