Crystal structures of fourteen halochalcogenylphos-pho-nium tetra-halogenidoaurates(III).

The structures of fourteen halochalcogenyl-phospho-nium tetra-halogen-ido-aurates(III), phosphane chalcogenide derivatives with general formula [R 1 3- nR 2 nPEX][AuX 4] (R 1 = t-butyl; R 2 = isopropyl; n = 0 to 3; E = S or Se; X = Cl or Br) are presented. The eight possible chlorido derivatives are: 17 a, n = 3, E = S; 18 a, n = 2, E = S; 19 a, n = 1, E = S; 20 a, n = 0, E = S; 21 a, n = 3, E = Se; 22 a, n = 2, E = Se; 23 a, n = 1, E = Se; and 24 a, n = 0, E = Se, and the corresponding bromido derivatives are 17 b-24 b in the same order. Structures were obtained for all compounds except for the tri-t-butyl derivatives 24 a and 24 b. Isotypy is observed for 18 a/18 b/22 a/22 b, 19 a/23 a, 17 b/21 b and 19 b/23 b. In eleven of the compounds, X⋯X contacts (mostly very short) are observed between the cation and anion, whereby the E-X⋯X groups are approximately linear and the X⋯X-Au angles approximately 90°. The exceptions are 17 a, 19 a and 23 a, which instead display short E⋯X contacts. Bond lengths in the cations correspond to single bonds P-E and E-X. For each group with constant E and X, the P-E-X bond-angle values increase monotonically with the steric bulk of the alkyl groups. The packing is analysed in terms of E⋯X, X⋯X (some between anions alone), H⋯X and H⋯Au contacts. Even for isotypic compounds, some significant differences can be discerned.

Crystal structures of ten phosphane chalcogenide complexes of gold(III) chloride and bromide.

The structures of ten phosphane chalcogenide complexes of gold(III) halides, with general formula R 1 3-n R 2 nPEAuX 3 (R 1 = t-butyl; R 2 = i-propyl; n = 0 to 3; E = S or Se; X = Cl or Br) are presented. The eight possible chlorido derivatives are: 9a, n = 3, E = S; 10a, n = 2, E = S; 11a, n = 1, E = S; 12a, n = 0, E = S; 13a, n = 3, E = Se; 14a, n = 2, E = Se; 15a, n = 1, E = Se; and 16a, n = 0, E = Se, and the corresponding bromido derivatives are 9b-16b in the same order. Structures were obtained for 9a, 10a (and a second polymorph 10aa), 11a (and its deutero-chloro-form monosolvate 11aa), 12a (as its di-chloro-methane monosolvate), 14a, 15a (as its deutero-chloro-form monosolvate 15aa, in which the solvent mol-ecule is disordered over two positions), 9b, 11b, 13b and 15b. The structures of 11a, 15a, 11b and 15b form an isotypic set, and those of compounds 10aa and 14a form an isotypic pair. All structures have Z' = 1. The gold(III) centres show square-planar coordination geometry and the chalcogenide atoms show approximately tetra-hedral angles (except for the very wide angle in 12a, probably associated with the bulky t-butyl groups). The bond lengths at the gold atoms are lengthened with respect to the known gold(I) derivatives, and demonstrate a considerable trans influence of S and Se donor atoms on a trans Au-Cl bond. Each compound with an isopropyl group shows a short intra-molecular contact of the type C-Hmethine⋯Xcis; these may be regarded as intra-molecular 'weak' hydrogen bonds, and they determine the orientation of the AuX 3 groups. The mol-ecular packing is analysed in terms of various short contacts such as weak hydrogen bonds C-H⋯X and contacts between the heavier atoms, such as X⋯X (9a, 10aa, 11aa, 15aa and 9b), S⋯S (10aa, 11a and 12a) and S⋯Cl (10a). The packing of the polymorphs 10a and 10aa is thus quite different. The solvent mol-ecules take part in C-H⋯Cl hydrogen bonds; for 15aa, a disordered solvent region at z ≃ 0 is observed. Structure 13b involves unusual inversion-symmetric dimers with Se⋯Au and Se⋯Br contacts, further connected by Br⋯Br contacts.

Crystal structures of sixteen phosphane chalcogenide complexes of gold(I) chloride, bromide and iodide.

The structures of 16 phosphane chalcogenide complexes of gold(I) halides, with the general formula R 1 3- nR 2 nPEAuX (R 1 = t-butyl; R 2 = isopropyl; n = 0 to 3; E = S or Se; X = Cl, Br or I), are presented. The eight possible chlorido derivatives are: 1a, n = 3, E = S; 2a, n = 2, E = S; 3a, n = 1, E = S; 4a, n = 0, E = S; 5a, n = 3, E = Se; 6a, n = 2, E = Se; 7a, n = 1, E = Se; and 8a, n = 0, E = Se, and the corresponding bromido derivatives are 1b-8b in the same order. However, 2a and 2b were badly disordered and 8a was not obtained. The iodido derivatives are 2c, 6c and 7c (numbered as for the series a and b). All structures are solvent-free and all have Z' = 1 except for 6b and 6c (Z' = 2). All mol-ecules show the expected linear geometry at gold and approximately tetra-hedral angles P-E-Au. The presence of bulky ligands forces some short intra-molecular contacts, in particular H⋯Au and H⋯E. The Au-E bond lengths have a slight but consistent tendency to be longer when trans to a softer X ligand, and vice versa. The five compounds 1a, 5a, 6a, 1b and 5b form an isotypic set, despite the different alkyl groups in 6a. Compounds 3a/3b, 4b/8b and 6b/6c form isotypic pairs. The crystal packing can be analysed in terms of various types of secondary inter-actions, of which the most frequent are 'weak' hydrogen bonds from methine hydrogen atoms to the halogenido ligands. For the structure type 1a, H⋯X and H⋯E contacts combine to form a layer structure. For 3a/3b, the packing is almost featureless, but can be described in terms of a double-layer structure involving borderline H⋯Cl/Br and H⋯S contacts. In 4a and 4b/8b, which lack methine groups, Cmeth-yl-H⋯X contacts combine to form layer structures. In 7a/7b, short C-H⋯X inter-actions form chains of mol-ecules that are further linked by association of short Au⋯Se contacts to form a layer structure. The packing of compound 6b/6c can conveniently be analysed for each independent mol-ecule separately, because they occupy different regions of the cell. Mol-ecule 1 forms chains in which the mol-ecules are linked by a Cmethine⋯Au contact. The mol-ecules 2 associate via a short Se⋯Se contact and a short H⋯X contact to form a layer structure. The packing of compound 2c can be described in terms of two short Cmethine-H⋯I contacts, which combine to form a corrugated ribbon structure. Compound 7c is the only compound in this paper to feature Au⋯Au contacts, which lead to twofold-symmetric dimers. Apart from this, the packing is almost featureless, consisting of layers with only translation symmetry except for two very borderline Au⋯H contacts.

Bromination and iodination of diphosphane dichalcogenides.

The diphosphane dichalcogenides dppmSe2, dppeSe2, diprpmSe2, diprpeSe2, dppmS2 and dppeS2, [dppm = bis(diphenylphosphano)methane, dppe = bis(diphenylphosphano)ethane, diprpm = bis(diisopropylphosphano)methane, diprpe = bis(diisopropylphosphano)ethane] have been treated with elemental bromine or iodine and the products 1-15 characterized by single crystal X-ray diffraction. DppeSe2 with bromine or iodine gives the simple (and previously known) adducts dppe(SeBr2)21 or dppe(SeI2)22 respectively; diprpeSe2 reacts similarly to give diprpe(SeBr2)23 (at 0 °C) or diprpe(SeI2)24. The bromine derivatives display a T-shaped geometry at selenium, whereas the iodine derivatives involve linear Se-I-I groups. With dppmSe2 and bromine, a product was formed at -50 °C, but could not be isolated; at room temperature the reaction leads to a mixture of products, from which only [dppmBr2]2+ [Se2Br10]2-5 (the anion involving a dibromine molecule coordinating to a Se centre) could be isolated. Reaction of dppeSe2 with excess bromine at room temperature leads to [dppeBr2]2+·½[SeBr6]2-·[SeBr2·Br2·Br3]-6. The reaction of dppmSe2 with iodine gives the 1 : 2 adduct [dppmSe2I]+ [I3]-7, the cation of which contains a novel five-membered CP2Se2 heterocycle. In a 1 : 1 ratio the same reaction gives another 1 : 2 adduct, [I2Se(dppm)Se-I-Se(dppm)SeI2]+ [I3]-8. DiprpmSe2 with iodine gives [diprpmSe2I]+ [I3]-9, analogous to 7, and with bromine at 0 °C the corresponding product [diprpmSe2Br]+ [Br3]-10. At room temperature, diprpeSe2 reacts with bromine to give a mixture of [diprpe(SeBr2)Br]+ Br-11 and [diprpeBr2]2+ [SeBr4]2-12, whereas diprpmSe2 forms [diprpmBr2]2+ [SeBr4]2-13, analogous to 12. The disulfides dppmS2 and dppeS2 react with bromine to give [dppmSBr]+ [Br3]-14 and [dppeSBr]+ [Br3]-15.

Correction: Synthesis and X-ray structural characterization of the (chlorochalcogeno)phosphonium cations R2R'PSCl+ and R2R'PSeCl+ as their AuCl4- salts.

Correction for 'Synthesis and X-ray structural characterization of the (chlorochalcogeno)phosphonium cations R2R'PSCl+ and R2R'PSeCl+ as their AuCl4- salts' by Daniel Upmann and Peter G. Jones, Dalton Trans., 2013, 42, 7526-7528.

Synthesis and X-ray structural characterization of the (chlorochalcogeno)phosphonium cations R2R'PSCl+ and R2R'PSeCl+ as their AuCl4- salts.

Phosphine chalcogenides R2R'PE react with (tht)AuCl to form complexes of the type R2R'PEAuCl (E = S, Se); stepwise oxidation with PhICl2 leads first to R2R'PEAuCl3 and then to the (chlorochalcogeno)phosphonium salts R2R'PECl(+)AuCl4(-).