Vibrational spectrum and structure of metal cyanide complexes in the solid state—V: K2Zn(CN)4, K2Cd(CN)4 and K2Hg(CN)4
01 Jan 1961-Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (Elsevier)-Vol. 17, Iss: 2, pp 188-200
TL;DR: In this article, the infrared spectra of single crystals of K2Zn(CN)4, K2Cd(CN), and K2Hg(CN)-4 have been observed and the authors have assigned all fundamental frequencies, except those of E-symmetry, for isolated ions.
About: This article is published in Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy.The article was published on 1961-01-01. It has received 65 citations till now. The article focuses on the topics: Valence (chemistry) & Infrared spectroscopy.
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TL;DR: In this article, a critical review of the preparation, characterization, and properties of cyanide complexes of the transition metals is provided, focusing on structural, thermodynamic, and kinetic data.
Abstract: Publisher Summary This chapter provides a critical review of the preparation, characterization (which is often incomplete), and properties of cyanide complexes of the transition metals. It focuses on structural, thermodynamic, and kinetic data. Two prominent features of transition metal cyanide chemistry are the wide range of metal:ligand ratios in complexes and the existence of many metals in low oxidation states. The chapter discusses the bearing of the physical state of metal cyanides on structural investigations. There are two important consequences of the fact that cyanide is an ion and not a neutral molecule: metal cyanides and their complexes are nonvolatile salts rather than volatile molecular entities and much of their chemistry is concerned with processes and measurements in solution in solvents of high complexing power, so that differences in complexing by solvent and ligand are involved. The chapter considers the effect of cyanide on the stabilities with respect to oxidation and reduction of metal ions in aqueous media, taking Fe(II) and Fe(III) as an example.
99 citations
TL;DR: In this paper, the vibrational spectroscopy of the pyramidal Fe(CN)2(CO) unit was investigated with respect to band positions and intensity ratios as influenced by counterion and solvent.
Abstract: The observation of nearly identical infrared spectra in the diatomic (2000 cm-1) region of oxidized forms of [NiFe]hydrogenases, as isolated from Chromatium vinosum (Happe et al. Nature 1997, 385, 126) and Desulfovibrio gigas (Volbeda et al. J. Am. Chem. Soc. 1996, 118, 12989) and the anion (η5-C5H5)Fe(CN)2(CO)- (Darensbourg et al. J. Am. Chem. Soc. 1997, 119, 7903), including isotopic label shifts, has prompted further development of the organometallic model complex as a spectroscopic reference. The vibrational spectroscopy of the pyramidal Fe(CN)2(CO) unit found in the salts of (η5-C5H5)Fe(CN)2(CO)- and (η5-C5Me5)Fe(CN)2(CO)- is thoroughly investigated with respect to band positions and intensity ratios as influenced by counterion and solvent. The neutral analogues (η5-C5H5)- and (η5-C5Me5)Fe(CN)(CO)2 as well as the protonated H[(η5-C5H5)Fe(CN)2(CO)] are included for comparison. The X-ray crystal structure of the latter finds short interionic N····N distances of 2.55 A indicative of CN-nitrogen protonat...
65 citations
TL;DR: In this article, two new benzene clathrates of the form Cd(Pyrazine)M(CN)4⁗C6H6, where M = Cd or Hg, have been prepared and their infrared and Raman spectra are reported.
Abstract: Two new benzene clathrates of the form Cd(Pyrazine)M(CN)4⁗C6H6, where M = Cd or Hg, have been prepared and their infrared and Raman spectra are reported.
33 citations
TL;DR: In this paper, ten new Hofmann-Td-type complexes of the form ML2M′(CN)4 (M = Mn, L = pyridine, α-, β- or γ-picoline, M′ = Zn) have been prepared, and their infrared and Raman spectra are reported.
21 citations
References
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TL;DR: In this article, the relation between the internuclear distances and force constants found for diatomic molecules is discussed, and it is shown that the relation can carry over to polyatomic molecules, with considerable accuracy.
Abstract: The relation between the internuclear distances and force constants found for diatomic molecules is discussed, and is shown to carry over to polyatomic molecules. It is shown that internuclear distances of polyatomic molecules can be predicted from vibrational data alone, with considerable accuracy.
596 citations
TL;DR: In this paper, the distribution of point symmetries within space groups and the population of the unit cell were used to derive selection rules for Raman and infra-red spectra of crystals.
Abstract: A method is described that permits deduction of selection rules for Raman and infra‐red spectra of crystals from a knowledge of just the space group designation and the population of the unit cell. When implemented by an appendix to this article showing, in a convenient arrangement, the distribution of point symmetries within space groups the method can be applied by a user familiar with point group manipulation but having no special knowledge of space groups. There are no selection rules operating in the liquid state. Some tentative qualitative conclusions are drawn concerning the relative intensities of certain kinds of components appearing in spectra of condensed systems. Sharpened selection rules are expected, and have been observed by others, to operate for single crystals containing non‐rotating molecules when these are given special orientations in the light path. These special orientations and the appropriate selection rules can be predicted from information mentioned above along with inspection of the external form of a crystal. All procedures have a desirable advantage of simplicity over prior ones directed toward the same ends.
393 citations
TL;DR: In this article, the rotation-vibration Hamiltonian has been expanded in order of order of magnitude and then subjected to two contact transformations, and these contact transformations were extended through the fourth order of approximation.
Abstract: In three previous papers of this series, the rotation‐vibration Hamiltonian has been expanded in orders of magnitude and then subjected to two contact transformations. These contact transformations, carried out thus far through the third order of approximation, are now extended through the fourth order of approximation.
142 citations
TL;DR: In this article, the infrared spectra of solid KAg(CN)2 and the mono-and di-substituted C13 and N15 species have been observed.
Abstract: The infrared spectra of solid KAg(CN)2 and the mono‐ and di‐substituted C13 and N15 species have been observed. The seven fundamental vibrations of the linear, symmetrical Ag(CN)2— ion have been assigned at 2146, 360, 2140, 390, 250, 310, and 107 cm—1 for the species containing C12 and N14.From the observed frequencies of the normal and isotopic species, force constants were calculated for two possible structures: N–C–Ag–C–N and C–N–Ag–N–C. It is shown that the latter structure gives unreasonable force constants, and that therefore the cyanides are probably bound to the silver through the carbon atom. Relative amplitudes of the atoms during the vibrations are shown.
64 citations
TL;DR: In this article, the infrared absorption spectrum of Ni(CO)4 has been studied in the liquid and gaseous states, and the frequency assignment changes have been made as a result of the observations.
Abstract: The infrared absorption spectrum of Ni(CO)4 has been studied in the liquid and gaseous states. As a result of the observations certain frequency assignment changes have been made. The most probable assignment of fundamental frequencies appears to be 2128 and 381 for the A1 species; 461 and 79 for the E species; 2057, 459, 422, and 79 for the F2 species; and 300 cm—1 for the F1 species. Using these values a normal coordinate treatment was carried out. Though the solution is not unique we can report FCO = 17.3±0.4 md/A and FNiC≈2.1 md/A.
57 citations