Vibrational Spectra and Structure of Complex Anions in Silicates. “Island” Structures

The complexes [cation] [Hg(SR)3](R = Me, cation = Et4N+; R = But, cation = Et4N+, Bu4N+, [N(Ph3P)2]+) have been prepared. The crystal structure of the methanethiolate complex shows that it contains centrosymmetric dinuclear anions [(MeS)2Hg(�-SMe)2Hg(SMe)2]2- with distorted tetrahedral geometry about the mercury atoms. Vibrational spectroscopic evidence suggests that this complex dissociates on dissolution in ethanol to give mononuclear [Hg(SMe)3]- species. The ButS- complexes appear to exist as mononuclear [Hg(SBut)3]- species both in the solid state and in solution. The metal-sulfur stretching frequencies are assigned for all of the complexes studied, and the vibrational spectra are discussed in terms of the structures of the complex anions involved. Crystal data for [(C2H5)4N]2Hg2(SCH3)6 : a 8.656(5), b gS130(6), c 12.368(8) �; α 102.16(4), β 105.51(4), γ 105.29(4)�; space group P1, Z 1, R 0.034, Rw 0.042.

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The Vibrational Spectra and Molecular Structure of Some Silver Pseudohalide Complex Anions.

Acta Chemica Scandinavica ◽

10.3891/acta.chem.scand.26-3579 ◽

1972 ◽

Vol 26 ◽

pp. 3579-3592 ◽

Cited By ~ 4

Author(s):

O. H. Ellestad ◽

P. Klæboe ◽

E. E. Tucker ◽

J. Songstad ◽

Åke Pilotti

Keyword(s):

Molecular Structure ◽

Vibrational Spectra ◽

Complex Anions

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RbAsF6, CsAsF6 und RbSbF6: Kristallstrukturen, Thermische Phasenumwandlungen und Schwingungsspektren / RbAsF6, CsAsF6 and RbSbF6: Crystal Structures, Thermal Phase Transitions, and Vibrational Spectra

Zeitschrift für Naturforschung B ◽

10.1515/znb-1998-0114 ◽

1998 ◽

Vol 53 (1) ◽

pp. 75-80 ◽

Cited By ~ 8

Author(s):

Caroline Röhr ◽

Sandra Loss

Keyword(s):

Phase Transitions ◽

Vibrational Spectra ◽

Structure Type ◽

Lattice Constants ◽

Cscl Type ◽

Thermal Phase ◽

Thermal Phase Transitions ◽

Fluorine Ions ◽

Alkaline Cations ◽

Complex Anions

The title compounds are isostructural to CsSbF6 and crystallize with the KOsF6 structure type (space group RS, Z = 3) with the lattice constants a = 749.7(1) pm, c = 758.9(1) pm (RbAsF6), a = 772.3(1) pm, c = 805.0(1) pm (CsAsF6) and a = 767.0(1) pm, c = 786.1(2) pm (RbSbF6). The structures exibit nearly ideal [MF6]– octahedra, the alkaline cations are coordinated by 12 fluorine ions in a distorted cuboctahedral geometry. Cations and complex anions form a slightly distorted CsCl arrangement. On heating, the arsenates transform to a NaCl arrangement with disordered [AsF6] ions, whereas the antimonates of Rb and Cs form the corresponding disordered CsCl type at higher temperatures. The phase transitions and the i. r. and Raman spectra as well as the structural relations to the remaining hexafluoropnictates AI[MVF6] are discussed.

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Complex halides of transition metals. Part VII. The vibrational spectra of the complex anions TiX62–, ZrX62–, and HfX62–, where X = Cl or Br

Journal of the Chemical Society A Inorganic Physical Theoretical ◽

10.1039/j19690000342 ◽

1969 ◽

Vol 0 (0) ◽

pp. 342-344 ◽

Cited By ~ 16

Author(s):

B. J. Brisdon ◽

G. A. Ozin ◽

R. A. Walton

Keyword(s):

Transition Metals ◽

Vibrational Spectra ◽

Complex Anions

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Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von (Ph3PNPPh3)[OsF5Cl]·CH2Cl2 und cis-(Ph3PNPPh3)[OsF4Cl2]·CH2Cl2 / Crystal Structures, Vibrational Spectra and Normal Coordinate Analysis of (Ph3PNPPh3) [OsF5Cl]·CH2Cl2 and cis-(Ph3PNPPh3 )[OsF4Cl2]·CH2Cl2

Zeitschrift für Naturforschung B ◽

10.1515/znb-2000-0109 ◽

2000 ◽

Vol 55 (1) ◽

pp. 45-50

Author(s):

B. Lorenzen ◽

W. Preetz

Keyword(s):

Single Crystals ◽

Vibrational Spectra ◽

Normal Coordinate Analysis ◽

Normal Coordinate ◽

Triclinic Space Group ◽

Space Group ◽

X Ray ◽

Structure Determinations ◽

Ir And Raman ◽

Complex Anions

By careful oxidation of the pure fluorochloroosmates(IV) with BrF3 in dichloromethane the mixed pentavalent complex anions [OsF5Cl]- and cis -[OsF4Cl2]- are formed. X-ray structure determinations on single crystals have been performed of (Ph3PNPPh3)[OsF5Cl]·CH2Cl2 (1) (triclinic, space group P1̄, a = 12.153(5), b = 12.387(5), c = 14.229(5) Å , α = 70.07(1), β = 65.46(1), γ = 72.87(1)°, Z = 2) and cis-(Ph3PNPPh3)[OsF4Cl2]·CH2Cl2 (2) (triclinic, space group P1̄, a = 11.987(2) b = 13.083(2), c = 14.456(2) Å, α = 66.30(1), β = 65.47(1), γ = 71.22(1)°, Z = 2). Based on the molecular parameters of the X-ray determinations the IR and Raman spectra for the anions of 1 and 2 have been assigned by normal coordinate analysis. Due to the mutual trans influences the valence force constants of asymmetrically coordinated octahedral axes F•-Os-Cl′ differ from those of the symmetric F-Os-F axes. The data are for 1: fd(OsF•) = 3.95, fd(OsF) = 4.07, fd(OsCl′) = 2.51 and for 2: fd(OsF•) = 3.45, fd(OsF) = 3.97, fd(OsCl′) = 2.42 mdyn/Å

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