Abstract
Both the partial molar volumes (V° 2m refractions (R° 2m ) of the solutes at infinite dilution have been determined at 20 °C for a series of six octahedral N6-coordinated cobalt(III) species featuring five coordinated ammonia ligands along with a sixth N-coordinated organonitrile of increasing ligand size (from acetonitrile to sebaconitrile). The experimental values for V° 2m are consistent with the relative sizes of the ligands but show larger values than those generated by computer modeling as the size of the cation increases, presumably due to the void space of the cation which increases with the size of the nitrile ligand.
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Fucaloro, A., Zanella, A., Widjaja, S., Widjaja, J.: Partial molar volumes and refractions of cobalt(III) complexes. Part 1: Homologous series of hexaaminecobalt(III) complexes. J. Solution Chem. 34, 1357–1370 (2005)
Balahura, R.J.: Preparation and characterization of nitrogen-bonded nitrile and amide complexes of pentaamminecobalt(III)-linkage isomers of cyanopyridine. Can. J. Chem. 52, 1762–1773 (1974)
Angus, P.M., Jackson, W.G.: Occurrence of neighboring group participation reactions in amide-N and amidine complexes derived from pentaammine(dinitrile)cobalt(III) Ions. Inorg. Chem. 35, 7196–7204 (1996)
Pinnell, R.P., Zanella, A.W., Kennedy, D.A., Kinsey, L.E., Neff, D.K.: Synthesis and reactivity of pentaammine-(organodinitrile)cobalt(III) and binuclear μ-decaammine-(organodinitrile)dicobalt(III) complexes. Manuscript in preparation
Hehre, W.H.: A Guide to Molecular Mechanics and Quantum Chemical Calculations, Wavefunction, Inc., Irvine, CA (2003), p. 102
Reference 5, p. 106.
Reference 5, p. 144
Herzberg, G.: Electronic Spectra and Electronic Structure of Polyatomic Molecules, Vol. 3. Van Nostrand, New York (1966), p. 631
Reference 8, p. 609
Hoy, A.R., Bunker, P.R.: A precise solution of the rotation bending Schrödinger equation for a triatomic molecule with application to the water molecule. J. Molec. Spec. 74, 1–8 (1979)
Amir-Ebrahim, V., Choplin, A., Demaison, J., Roussy, G.: Microwave spectrum of the carbon-13 ring-monosustituted toluenes and structure of toluene. J. Molec. Spec. 89, 42–52 (1981)
Reference 8, p. 640
Redlich, O., Rosenfeld, P.: The partial molar volume of dissolved electrolyte. I. Z. Physik. Chem. A155, 65–74 (1931)
Redlich, O., Meyer, D.M.: The molal volumes of electrolytes. Chem. Rev. 64, 221–227 (1964)
Millero, F.J.: Partial molal volumes of electrolytes in aqueous solutions. In: Horne, R.A. (ed.) Water and Aqueous Solutions: Structure, Thermodynamics, and Transport Properties, p. 521. Wiley-Interscience, New York (1972)
Fucaloro, A.F.: Reporting molar refractions. J. Solution Chem. 31, 601–605 (2002)
Fucaloro, A.F.: Partial molar volumes from refractive index measurements. J. Chem. Educ. 79, 865–868 (2002)
Taylor, W.J.: Apparent and partial molar polarizations in solutions and the Halverstadt-Kumler and Hedestrand equations. J. Phys. Chem. 79, 1817–1820 (1975)
Reference 15, p. 525
Vogel, A.I.: Physical properties and chemical constitution. XXIII. Miscellaneous compounds. Investigation of the so-called co.ovrddot.ordinate or dative link in esters of oxy acids and in nitro paraffins by molecular refractivity determinations. Atomic, structural, and group parachors and refractivities. J. Chem. Soc. 1833–1855 (1948) and references cited therein
Drude, P., Nernst, W.: Über Elektrostriktion durch Freie Ionen. Z. Physik. Chem. (Frankfurt) 15, 79–85 (1894)
CRC Handbook of Chemistry and Physics, 73rd ed.; D. R. Lide, ed., CRC Press, Boca Raton, FL (1992)
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Fucaloro, A., Pinnell, R., Zanella, A. et al. Partial Molar Volumes and Refractions of Cobalt(III) Complexes, Part 2: Homologous Series of Nitrilopentaamminecobalt(III) Complexes. J Solution Chem 35, 1245–1254 (2006). https://doi.org/10.1007/s10953-006-9055-8
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DOI: https://doi.org/10.1007/s10953-006-9055-8