Molecular Orbital Studies Of The Dipole Moments Of Methyl Substituted Amines, Phosphines, And Their Borane Adducts

dc.creatorKuznesof P.M.
dc.creatorPessine F.B.T.
dc.creatorBruns R.E.
dc.creatorShriver D.F.
dc.date1975
dc.date2015-06-26T17:51:11Z
dc.date2015-11-26T14:23:45Z
dc.date2015-06-26T17:51:11Z
dc.date2015-11-26T14:23:45Z
dc.date.accessioned2018-03-28T21:25:48Z
dc.date.available2018-03-28T21:25:48Z
dc.identifier
dc.identifierInorganica Chimica Acta. , v. 14, n. C, p. 271 - 280, 1975.
dc.identifier201693
dc.identifier10.1016/S0020-1693(00)85754-0
dc.identifierhttp://www.scopus.com/inward/record.url?eid=2-s2.0-49549143663&partnerID=40&md5=23b628b92f6831a3657d7c4519bc8c88
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/96598
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/96598
dc.identifier2-s2.0-49549143663
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1245209
dc.descriptionThe magnitudes and trends of the dipole moments of MexH3-xE and MexH3-xEBH3 (E = N, P; x = 0→3; Me = CH3) were investigated via CNDO-MO methods. Moments evaluated by the CNDO/2D approach reproduced the experimental data better than the strict CNDO/2 formalism. Transformation of the canonical CNDO/2 MO's to localized MO's (LMO's) permitted a partitioning of the total moments into bond moments, bond polarization moments, and lone pair moments. Values of the lone pair moments of the phosphines are calculated to be greater than those of the amines. Within the framework of the CNDO/2D approximation, coordination of BH3 to H3N involves a charge migration primarily between the N-bound and B-bound hydrogens (0.33e) while coordination to H3P is primarily P → B (0.27e). The covalent character of the BN and BP bonding LMO's is 46 and 61%, respectively. The CNDO molecular orbital results are in general agreement with Weaver and Parry's model for dipole moments and base strengths of amines and phosphines. © 1975.
dc.description14
dc.descriptionC
dc.description271
dc.description280
dc.descriptionPresented at the XXV Annual Meeting of the Sociedade Brasileira para o Progresso da Ciencia. Abstract no. 27-C1, Ciěncia Cult., 25, S91 (1973). Abstracted, in part, from the M.S. thesis of F.B.T.P. b, Campinas. c) EvanstonWeaver, Parry, (1966) Inorg. Chem., 5, p. 703
dc.descriptionKodama, Weaver, LaRochelle, Parry, Dipole Moment Studies II. The Dipole Moments of the Ethylphosphines (1666) Inorganic Chemistry, 5, p. 710
dc.descriptionWeaver, Parry, Dipole Moment Studies. III. The Dipole Moments of the Methylamine Boranes (1966) Inorganic Chemistry, 5, p. 713
dc.descriptionWeaver, Parry, Dipole Moment Studies. IV. Trends in Dipole Moments (1966) Inorganic Chemistry, 5, p. 718
dc.descriptionMorse, Parry, Dipole Moment Studies. V. The Dipole Moments of the Methylphosphine Boranes (1972) The Journal of Chemical Physics, 57, p. 5365
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dc.descriptionShillady, (1970) Ph.D. Thesis, , University of Virginia
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dc.descriptionHillier, Saunders, An ab initio study of the bonding in phosphine borane, trifluorophosphine broane and trifluorophosphine oxide (1971) Journal of the Chemical Society A: Inorganic, Physical, Theoretical, p. 664. , ab initio F3PBH3 and H3PBH3
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dc.descriptionAslangul, Veillard, Daudel, Gallais, (1971) Theoret. Chim. Acta., 23, p. 211. , ab initio H3NBH3
dc.descriptionTinland, An ab initio SCF-LCAO-MO study of the electronic structure of borazane, BH3NH3 (1969) Journal of Molecular Structure, 3, p. 244. , ab initio
dc.descriptionPeyerimhoff, Buenker, Further Study of Umbrella vs Bridged Geometries: SCF–MO and CI Calculations for C2H6++ and Ammonia Borane (1968) The Journal of Chemical Physics, 49, p. 312. , ab initio, H3NBH3
dc.descriptionMoireau, Veillard, (1968) Theoret. Chim. Acta., 11, p. 344. , ab initio H3NBH3
dc.descriptionVeillard, Levy, Daudel, Gallais, (1967) Theoret. Chim. Acta., 8, p. 312. , ab initio, H3NBH3
dc.descriptionKuznesof, Shriver, (1968) J. Am. Chem. Soc., 90, p. 1683. , CNDO
dc.descriptionKuznesof, (1967) Ph.D. Dissertation, , Northwestern University, preliminary study (CNDO) of the dipole moments of the methylamine boranes is presented here
dc.descriptionHoffmann, Theoretical Investigations on Boron-Nitrogen Molecules (1964) Adv. Chem. Ser., 42, p. 78
dc.descriptionHoffmann, (1964) J. Chem. Phys., 40, p. 2474. , Extended Hückel, H3NBH3
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dc.descriptionR.E. Bruns, Quantum Chemistry Program Exchange, Department of Chemistry, Indiana University, Bloomington Indiana program no 240Santry, (1968) J. Am. Chem. Soc., 90, p. 3309
dc.descriptionP.M. Kuznesof, submitted to QCPE. A listing is available on request. The localization procedure follows the ERTS method (refs. 7a, c) and, furthermore, is faster than a similar sub-program LOCAL currently available from QCPE (no. 191). Incorporation of ORLOC into CINDOM or CNINDO (QCPE no. 141) involves the same changes as incorporation of LOCAL into CNINDO. Another significant advantage of ORLOC is that it does not require the introduction of any additional matrices as does LOCAL. ORLOC is also available from the author as an independent program requiring as input only the CMO's and coulomb repulsion integralsP.M. Kuznesof, Quantum Chemistry Program Exchange, Departrnent of Chemistry, Indiana University, Bloomington, Indiana, program no. 94Boyd, (1972) J. Am. Chem. Soc., 94, p. 64
dc.descriptionPople, Segal, (1965) J. Chem. Phys., 43, p. S136
dc.descriptionOdom, Barnes, Hudgens, Durig, (1974) J. Phys. Chem., 78, p. 1503. , A geometry optimized CNDO/2 calculation on Me3NBH3 gives a dipole moment in excellent numerical agreement with the experimental value. Geometry optimization of Me3N, however, yields essentially no improvement. See
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dc.descriptionThese authors used WP's estimate for the P-=CH3 moment and they settled on the range 3.4- 4.0D for the P-BH3 moment because of an ambiguity arising in their estimate of this moment in CH3PH2BH3. For this molecule they calculated 3.92 and 3.44D depend- ing on which dipole components they selected for their analysisStamper, Trinajastic, Localised orbitals for some simple molecules (1967) Journal of the Chemical Society A: Inorganic, Physical, Theoretical, p. 782. , Values for the nitrogen lone pair moment in NH3 have been previously reported, ranging from 3.4 to 3.8D depending on the starting SCF-CMO's. See
dc.descriptionPeters, 764. Localised molecular orbitals in self-consistent field wave functions. Part III. Hybridisations, atomic charges, and dipole moments in non-linear molecules (1963) Journal of the Chemical Society (Resumed), p. 4017
dc.descriptionPeters, Localised molecular orbitals in self-consistent field wave functions. Part X. The nature of electronegativity (1966) Journal of the Chemical Society A: Inorganic, Physical, Theoretical, p. 656. , Peters has carried out extensive studies regarding the nature and applicability of LMO's. See, and references therein
dc.descriptionCoulson, (1961) Valence, p. 218. , 2nd ed., Oxford University Press, London
dc.descriptionSchaefer, III, (1972) The Electronic Structure of Atoms and Molecules, p. 197. , Addison-Wesley, Reading, Mass
dc.descriptionCNDO/2 results obtained for H3PBH3 and Me3PBH3 using their experimental geometries did not significantly differ from the results presented in this workVan Wazer, Callis, Shoolery, Jones, (1956) J. Am. Chem. Soc., 78, p. 5715
dc.descriptionWe define percentage covalent character as where the summation is over the atomic orbitals of atoms R, S, or bothBrauman, Blair, The bicyclo[3.2.2]nonatrienyl anion. The anionic analog of the norbornadienyl cation (1968) Journal of the American Chemical Society, 90, p. 6562
dc.descriptionBrauman, Riveros, Blair, (1971) J. Am. Chem. Soc., 93, p. 3914
dc.descriptionMcDaniel, Coffman, Strong, (1970) J. Am. Chem. Soc., 92, p. 6697
dc.descriptionHoltz, Beauchamp, (1969) J. Am. Chem. Soc., 91, p. 5913
dc.descriptionBeauchamp, Ion Cyclotron Resonance Spectroscopy (1971) Annual Review of Physical Chemistry, 22, p. 527
dc.descriptionSantry, Segal, (1967) J. Chem. Phys., 47, p. 158. , phosphines
dc.descriptionWatanabe, (1957) J. Chem. Phys., 26, p. 542. , amines
dc.languageen
dc.publisher
dc.relationInorganica Chimica Acta
dc.rightsfechado
dc.sourceScopus
dc.titleMolecular Orbital Studies Of The Dipole Moments Of Methyl Substituted Amines, Phosphines, And Their Borane Adducts
dc.typeArtículos de revistas


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