Phenylchloroantimon(III)ates; their preparations, and the crystal structures of Me4N[PhSbCl3], [Hpy]2[PhSbCl4], and Me4N[Ph2SbCl2]
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Phenylantimony dichloride reacts with ionic chlorides such as Me4NCl or HpyCl to give salts of both the [PhSbCl3]- and [PhSbCl4]2- anions, whereas the related diphenylantimony chloride will accept only one chloride ion to give [Ph2SbCl2]- salts. Under similar conditions, no anionic products are formed from Ph3Sb. These results can be rationalised if chloride ion addition takes place trans to antimonychlorine bonds in the starting material and the negative charge is delocalised via three-centre bonding in the resulting ClSb⋯Cl- system. Structures have been determined by single crystal X-ray diffraction for Me4N[PhSbCl3] (a 9.214(5), b 11.499(5), c 16.179(6) Å, β 121.65(5)°, space group P21/c), [Hpy]2[PhSbCl4] (a 8.549(5), b 8.899(5), c 14.509(6) Å, α 100.16(5), β 90.09(4), γ 114.69(5)°, space group P1) and Me4N[Ph2SbCl2] (a 12.255(5), b 11.078(5), c 14.200(6) Å, β 112.28(5)°, space group P21/n). Me4N[PhSbCl3] contains a centrosymmetric, double chlorine-bridged dimeric anion, while the anions in both the [PhSbCl4]- and [Ph2SbCl2]- salts are monomeric. Antimonychlorine bond distances are discussed in terms of the delocalisation picture mentioned above. © 1988.
author list (cited authors)
Hall, M., & Sowerby, D. B.