Substituted methanes

Palma, Brother Francis E.; Piotrowski, Edward A.; Cleveland, Forrest F.

doi:10.1016/0022-2852(64)90061-x

Cited by 36 publications

(8 citation statements)

References 19 publications

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“…Our measurements for CDaCI 2 and CHDC12 agree quite well with the infrared results given by Palma et aL [12], except again for v 5 of CD2C12, which is not visible in the infra-red.…”

Section: Raman Intensities Of Dichloromethanessupporting

confidence: 86%

“…With respect to the potential function, we have found only one paper, by Shimanouchi and Suzuki [11], in which these authors evaluate both a Urey-Bradley force field (UBFF) and the general harmonic force field (GHFF) from their own infra-red data on the three isotopic species mentioned above. We would like to note that the fundamental wavenumbers of CHDCI~ are directly related to those of CHzC12 and CD2Cl~ by a complete isotopic rule, as was in fact shown by Palma et al [12] as a check of their assignment, and therefore do not provide independent data for a least squares refinement process. Thus, for the four-dimensional A 1 362 R. Escribano et al Photographic detection and mercury lamp as exciting source.…”

mentioning

confidence: 94%

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Absolute Raman intensities, force constants, and electro-optical parameters of CH₂Cl₂, CD₂Cl₂ and CHDCl₂

et al. 1979

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The absolute Raman intensities and depolarization ratios of all the fundamental bands of CH2C12, CD~CI~ and CHDCI~ have been measured in the gas phase. These experimental data have been included in a refinement of the vibrational potential function of the dichloromethanes. A detailed description is made of the use of the bond polarizability approach. Explicit expressions for the derivatives of the molecular polarizability with respect to the symmetry coordinates are given in terms of the zeroth-and first-order electrooptical parameters of the theory. Good agreement is found between experimental and calculated intensities. The refined electro-optical parameters compare quite well with those obtained from methane, chloroform and carbon tetrachloride. The derivatives of the molecular polarizability with respect to the normal coordinates are also given.

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“…Our measurements for CDaCI 2 and CHDC12 agree quite well with the infrared results given by Palma et aL [12], except again for v 5 of CD2C12, which is not visible in the infra-red.…”

Section: Raman Intensities Of Dichloromethanessupporting

confidence: 86%

mentioning

confidence: 94%

Absolute Raman intensities, force constants, and electro-optical parameters of CH₂Cl₂, CD₂Cl₂ and CHDCl₂

et al. 1979

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“…Dies erhärtet die Ergebnisse von Plyler et al und Shimanouchi et al, wonach die Intensität der asymmetrischen C-H Streckschwingung vq im Gaszustand vernachlässigbar ist. Im flüssigen Zustand tritt die vq-Absorption jedoch zweifelsfrei und mit einer der n-Schwingung vergleichbaren Absorptionsintensität auf [10].…”

Section: Diskussionunclassified

“…Über Zuordnungsschwierigkeiten der IR-Absorption im Bereich der CH2-Biegeschwingung von gasförmigem CH2CI2 berichten Palma et al [10]. Sie vermuten, daß v2 im Gaszustand eine verschwindende Intensität besitzt, denn die bei 1467 cm -1 auftretende Bande kann vo nicht zugeordnet werden, da dies eine außergewöhnlich große langwellige Verschiebung des Bandenmaximums um mehr als 40 cm -1 beim Übergang vom gasförmigen zum flüssigen Zustand voraussetzt (r2(max) liegt in flüssigem CH2CI2 bei 1423 cm -1 ).…”

Section: Diskussionunclassified

“…Sie vermuten, daß v2 im Gaszustand eine verschwindende Intensität besitzt, denn die bei 1467 cm -1 auftretende Bande kann vo nicht zugeordnet werden, da dies eine außergewöhnlich große langwellige Verschiebung des Bandenmaximums um mehr als 40 cm -1 beim Übergang vom gasförmigen zum flüssigen Zustand voraussetzt (r2(max) liegt in flüssigem CH2CI2 bei 1423 cm -1 ). Die Absorption in gasförmigem CH2CI2 im Biegeschwingungsbereich um 1450 cm -1 wird im wesentlichen Kombinations-und Obertönen von C-Cl Streckschwingungen zugeschrieben [10].…”

Section: Diskussionunclassified

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Infrarotabsorption von reinem Dichlormethan bis zu hohen Drücken und Temperaturen / Infrared Absorption of Pure Dichloromethane Measured up to High Pressures and Temperatures

Buback

Franck

Lendlc

1979

Zeitschrift Für Naturforschung A

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Infrared Absorption of Pure Dichloromethane Measured up to High Pressures and TemperaturesThe infrared absorption of the v\ and re stretching fundamentals and of the j>2 CH2-bending mode in pure dichloromethane has been measured up to pressures and temperatures of 2 kbar and 200 °C, respectively. The optical high pressure cells were equipped with CaF2 single crystal windows. The applicability of this window material at high pressures and temperatures was investigated.With increasing density the wavenumbers of maximum absorption of ri and i'2 shift to lower and of i'6 to higher values. The integrated molar absorptivity of J>2 and v6 increases with increasing density while it remains nearly constant for the vibration. The results obtained for the C-H modes clearly differ from those measured for O-H or N-H vibrations in polar materials. They are attributed to the action of repulsive forces in dense CH2C12.

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Silver(I) Complexes of the Weakly Coordinating Solvents SO₂ and CH₂Cl₂: Crystal Structures, Bonding, and Energetics of [Ag(OSO)][Al{OC(CF₃)₃}₄], [Ag(OSO)_2/2][SbF₆], and [Ag(CH₂Cl₂)₂][SbF₆]

Decken

Knapp

Nikiforov

et al. 2009

Chemistry A European J

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Pushing the limits of coordination chemistry: The most weakly coordinated silver complexes of the very weakly coordinating solvents dichloromethane and liquid sulfur dioxide were prepared. Special techniques at low temperatures and the use of weakly coordinating anions allowed structural characterization of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(Cl(2)CH(2))(2)][SbF(6)] (see figure). An investigation of the bonding shows that these complexes are mainly stabilized by electrostatic monopole-dipole interactions.The synthetically useful solvent-free silver(I) salt Ag[Al(pftb)(4)] (pftb=--OC(CF(3))(3)) was prepared by metathesis reaction of Li[Al(pftb)(4)] with Ag[SbF(6)] in liquid SO(2). The solvated complexes [Ag(OSO)][Al(pftb)(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)] were prepared and isolated by special techniques at low temperatures and structurally characterized by single-crystal X-ray diffraction. The SO(2) complexes provide the first examples of coordination of the very weak Lewis base SO(2) to silver(I). The SO(2) molecule in [Ag(OSO)][Al(pftb)(4)] is eta(1)-O coordinated to Ag(+), while the SO(2) ligands in [Ag(OSO)(2/2)][SbF(6)] bridge two Ag(+) ions in an eta(2)-O,O' (trans,trans) manner. [Ag(CH(2)Cl(2))(2)][SbF(6)] contains [Ag(CH(2)Cl(2))(2)](+) ions linked through [SbF(6)](-) ions to give a polymeric structure. The solid-state silver(I) ion affinities (SIA) of SO(2) and CH(2)Cl(2), based on bond lengths and corresponding valence units in the corresponding complexes and tensimetric titrations of Ag[Al(pftb)(4)] and Ag[SbF(6)] with SO(2) vapor, show that SO(2) is a weaker ligand to Ag(+) than the commonly used weakly coordinating solvent CH(2)Cl(2) and indicated that binding strength of SO(2) to silver(I) in the silver(I) salts increases with increasing size of the corresponding counteranion ([Al(pftb)(4)](-)>[SbF(6)](-)). The experimental findings are in good agreement with theoretical gas-phase ligand-binding energies of [Ag(L)(n)](+) (L=SO(2), CH(2)Cl(2); n=1, 2) and solid-state enthalpies obtained from Born-Fajans-Haber cycles by using the volume-based thermodynamics (VBT) approach. Bonding analysis (VB, NBO, MO) of [Ag(L)(n)](+) suggests that these complexes are almost completely stabilized by electrostatic interaction, that is, monopole-dipole interaction, with almost no covalent contribution by electron donation from the ligand orbitals into the vacant 5s orbital of Ag(+). All experimental findings and theoretical considerations demonstrate that SO(2) is less covalently bound to Ag(+) than CH(2)Cl(2) and support the thesis that SO(2) is a polar but non-coordinating solvent towards Ag(+).

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Substituted methanes

Cited by 36 publications

References 19 publications

Absolute Raman intensities, force constants, and electro-optical parameters of CH₂Cl₂, CD₂Cl₂ and CHDCl₂

Absolute Raman intensities, force constants, and electro-optical parameters of CH₂Cl₂, CD₂Cl₂ and CHDCl₂

Infrarotabsorption von reinem Dichlormethan bis zu hohen Drücken und Temperaturen / Infrared Absorption of Pure Dichloromethane Measured up to High Pressures and Temperatures

Silver(I) Complexes of the Weakly Coordinating Solvents SO₂ and CH₂Cl₂: Crystal Structures, Bonding, and Energetics of [Ag(OSO)][Al{OC(CF₃)₃}₄], [Ag(OSO)_2/2][SbF₆], and [Ag(CH₂Cl₂)₂][SbF₆]

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Substituted methanes

Cited by 36 publications

References 19 publications

Absolute Raman intensities, force constants, and electro-optical parameters of CH2Cl2, CD2Cl2 and CHDCl2

Absolute Raman intensities, force constants, and electro-optical parameters of CH2Cl2, CD2Cl2 and CHDCl2

Infrarotabsorption von reinem Dichlormethan bis zu hohen Drücken und Temperaturen / Infrared Absorption of Pure Dichloromethane Measured up to High Pressures and Temperatures

Silver(I) Complexes of the Weakly Coordinating Solvents SO2 and CH2Cl2: Crystal Structures, Bonding, and Energetics of [Ag(OSO)][Al{OC(CF3)3}4], [Ag(OSO)2/2][SbF6], and [Ag(CH2Cl2)2][SbF6]

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Absolute Raman intensities, force constants, and electro-optical parameters of CH₂Cl₂, CD₂Cl₂ and CHDCl₂

Absolute Raman intensities, force constants, and electro-optical parameters of CH₂Cl₂, CD₂Cl₂ and CHDCl₂

Silver(I) Complexes of the Weakly Coordinating Solvents SO₂ and CH₂Cl₂: Crystal Structures, Bonding, and Energetics of [Ag(OSO)][Al{OC(CF₃)₃}₄], [Ag(OSO)_2/2][SbF₆], and [Ag(CH₂Cl₂)₂][SbF₆]