First Anhydrous Gold Perchlorato Complex: ClO₂Au(ClO₄)₄. Synthesis and Molecular and Crystal Structure Analysis

Abstract

Chlorine trioxide, Cl(2)O(6), reacts with Au metal, AuCl(3), or HAuCl(4).nH(2)O to yield the well-defined chloryl salt, ClO(2)Au(ClO(4))(4). The crystal and molecular structure of ClO(2)Au(ClO(4))(4) was solved by a Rietveld analysis of powder X-ray diffraction data. The salt crystallizes in a monoclinic cell, space group C2/c, with cell parameters a = 15.074(5), b = 5.2944(2), and c = 22.2020(2) A and beta = 128.325(2) degrees. The structure displays discrete ClO(2)(+) ions lying in channels formed by Au(ClO(4))(4)(-) stacks. Au is located in a distorted square planar environment: Au-O = 1.87 and 2.06 A. [ClO(4)] groups are monodentate with ClO(b) = 1.53 and ClO(t) = 1.39 A (mean distances; O(b), oxygen bonded to Au; O(t), free terminal oxygen). A full vibrational study of the Au(ClO(4))(4)(-) anion is supported by DFT calculations.

Reactions of ClF3 with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates

“…The experimental and calculated vibrational frequencies are listed in Table 8. Similar vibrational frequencies were reported for [ClO 2 ] + in compounds such as [ClO 2 ][GeF 5 ], [ClO 2 ][ M F 6 ] ( M =Ru, Pt, Au, Sb), [ClO 2 ][ClO 4 ], [ClO 2 ][Cd(ClO 4 ) 3 ], [ClO 2 ][Au(ClO 4 ) 4 ] and [ClO 2 ][ M (ClO 4 ) 4 ] ( M =In, Tl) [34,37,40,42,43,115–118] . This indicates a minor effect of the anions and bridging atoms (O or F) on the vibrational frequencies of the [ClO 2 ] + cation.…”

“…In our quantum‐chemical calculations, we also obtain angles below 120°. However, in [ClO 2 ][Au(ClO 4 ) 4 ] and [ClO 2 ][Sb 2 F 11 ], the O−Cl−O angles were reported with 132(3) and 121.9(15)°, respectively, likely due to the quality of the structure determinations [37,44] …”

“…Compounds with [ClO 2 ] + or [BrO 2 ] + ions are furthermore obtained when X O 3 F ( X =Cl, Br) is reacted with strong Lewis acids [34] . In the case of [ClO 2 ] + cations, reactions of Cl 2 O 6 (“[ClO 2 ][ClO 4 ]”) with metals or chlorides often lead to the formation of dioxychloronium(V) perchloratometallates, where [ClO 4 ] − anions are bound as ligands [35–40] . Crystal structures of [ClO 2 ] + salts with the following anions have been reported: [BF 4 ] − , [GeF 2/2 F 4/1 ] − , [RuF 6 ] − , [SbF 6 ] − , [Sb 2 F 11 ] − , [ClO 4 ] − , [Au(ClO 4 ) 4 ] − and [Sn(ClO 4 ) 6 ] 2− [34,37–44] .…”

“…In the case of [ClO 2 ] + cations, reactions of Cl 2 O 6 (“[ClO 2 ][ClO 4 ]”) with metals or chlorides often lead to the formation of dioxychloronium(V) perchloratometallates, where [ClO 4 ] − anions are bound as ligands [35–40] . Crystal structures of [ClO 2 ] + salts with the following anions have been reported: [BF 4 ] − , [GeF 2/2 F 4/1 ] − , [RuF 6 ] − , [SbF 6 ] − , [Sb 2 F 11 ] − , [ClO 4 ] − , [Au(ClO 4 ) 4 ] − and [Sn(ClO 4 ) 6 ] 2− [34,37–44] . Recently, compounds were published containing the complex [Cl 2 BrO 6 ] + cation that might be considered as a central [BrO 2 ] − anion coordinating to two [ClO 2 ] + cations [45] …”

Square‐Planar Noble Metal Iodate [M(IO3)4]n– (M = PdII, AuIII; n = 2, 1) Anions and Their Ability to Form Polar and Centrosymmetric Architectures

“…[16] We have surveyed 28 high-resolution iodate crystal structures to arrive at a value of 1.792 (5) 4 ], [17] [18] and (ClO 2 )[Au(ClO 4 ) 4 ]. [19] In all three examples significant lengthening of the bridging E-O (E = N, Cl) bonds is observed. Short contacts on the order of 2.5 to 2.8 Å between the oxygen atom from one iodate anion and the iodine atom of a neighboring iodate play a critical role in the structures of iodate compounds and minerals.…”