Pentafluorophenylarsines. The crystal and molecular structures of tetrakis(pentafluorophenyl)diarsine, (C6F5)2AsAs(C6F5)2, tetrakis(pentafluorophenyl)diarsenic(III) oxide, (C6F5)2AsOAs(C6F5)2, and tris(pentafluorophenyl)arsine

Add time:08/12/2019    Source:sciencedirect.com

Crystalline materials from a high-boiling fraction obtained as by-products in the preparation of C6F5AsCl2, or from subsequent reaction with elemental mercury, have been crystallographically identified as consisting primarily of secondary and tertiary substituted pentafluorophenylarsenic compounds. The crystal and molecular structures of three of these products are reported: (C6F5)2AsAs(C6F5)2 (1), (C6F5)2AsOAs(C6F5)2 (2), and (C6F5)3As (3). 1: C24F20As2, tetragonal, P421c, a 13.253(3), c 42.584(10) Å, V 7479 Å3, Z = 12 (three independent half-molecules), R(F) 6.54%. 2: C24F20As2O, monoclinic, C2/c, a 16.676(5), b 7.755(2), c 22.266(6) Å, β 117.13(2)°, V 2563 Å3, Z = 4 (one half-molecule), R(F) 4.85%. 3: C18F15As, triclinic, P1, a 8.902(2), b 10.888(2), c 11.185(2) Å, α 109.59(2), β 103.12(2), γ 106.95° V 911.3(4) Å3, R(F) 4.50%. 1 is twisted 16.5° from a trans conformation and contains the longest AsAs bond reported for any organoarsenic compound, 2.479(4) Å. However, non-bonded F…F contact distances fail to support steric reasons for these distortions. 2 has an AsOAs angle fo 116.2(3)° determined primarily by lattice packing effects. 3 is pyramidal with AsC distances and CAsC angles typical of triarylarsines.

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