Halogen Bonding in the Gas Phase: A Comparison of the Iodine Bond in B?ICl and B?ICF 3 for Simple Lewis Bases B

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• 关键词：Ab initio calculations ; Angular and radial geometry ; Intermolecular force constants ; Iodine bond ; Iodine monochloride ; Iodo ; trifluoromethane ; Lewis bases ; Potential energy functions ; Rotational spectroscopy
• 刊名：Topics in Current Chemistry
• 出版年：2015
• 出版时间：2015
• 年：2015
• 卷：358
• 期：1
• 页码：43-77
• 全文大小：980 KB
• 参考文献：1. Davey JB, Legon AC, Waclawik ER (2000) Measurement of inter- and intramolecular charge transfer in the complex N₂?ICl from analysis of halogen nuclear quadrupole hyperfine structure in the rotational spectrum. J Mol Struct 500:391-02 CrossRef
  2. Davey JB, LegonAC, Waclawik ER (1999) Inter- and intra-molecular electron transfer in the complex OC?ICl determined from iodine and chlorine nuclear quadrupole hyperfine structure in its rotational spectrum. Phys Chem Chem Phys 1:3097-102
  3. Davey JB, Legon AC (1999) Rotational spectroscopy of mixtures of ethyne and iodine monochloride: isolation and characterisation of the π-type complex C₂H₂?ICl. Phys Chem Chem Phys 1:3721-726 CrossRef
  4. Thumwood JMA, Legon AC (1999) A π-electron donor-acceptor complex of ethene and iodine monochloride: geometry, binding strength and charge redistribution determined by rotational spectroscopy. Chem Phys Letts 310:88-6 CrossRef
  5. Davey JB, Legon AC, Waclawik ER (2000) An investigation of the gas-phase complex of water and iodine monochloride by microwave spectroscopy: geometry, binding strength and electron redistribution. Phys Chem Chem Phys 2:1659-665 CrossRef
  6. Legon AC, Waclawik ER (1999) Angular geometry, binding strength and charge transfer for the complex H₂S?ICl determined by rotational spectroscopy. Chem Phys Letts 312:385-93 CrossRef
  7. Herrebout WA, Legon AC, Waclawik ER (1999) Is there a significant intermolecular charge transfer in the ground state of the HCN?ICl complex? An answer from rotational spectroscopy. Phys Chem Chem Phys 1:4961-966 CrossRef
  8. Waclawik ER, Legon AC (1999) Halogen nuclear quadrupole coupling in the rotational spectrum of H₃N?ICl as a probe of inter- and intramolecular transfer. Phys Chem Chem Phys 1:4695-700 CrossRef
  9. Davey JB, Legon AC, Waclawik ER (2000) Inter- and intramolecular electronic transfer on formation of H₃P?ICl as determined by rotational spectroscopy. Phys Chem Chem Phys 2:2265-269 CrossRef
  10. Anable JP, Hird DE, Stephens SL, Zaleski DP, Walker NR, Legon AC (2014) The rotational spectrum of N₂?ICF₃ observed with a broadband, chirped-pulse FT microwave spectrometer. Manuscript in preparation
  11. Stephens SL, Walker NR, Legon AC (2011) Rotational spectra and properties of complexes B?ICF₃ (B=Kr or CO) and a comparison of the efficacy of ICl and ICF₃ as iodine donors in halogen bond formation. J Chem Phys 135:224309 CrossRef
  12. Stephens SL, Walker NR, Legon AC (2014) Broadband rotational spectroscopy of the ethyne?ICF₃ complex in the microwave region. Manuscript in preparation
  13. Stephens SL, Mizukami W, Tew DP, Walker NR, Legon AC (2012) The halogen bond between ethene and a simple perfluoroiodoalkane: C₂H₄?ICF₃ identified by broadband rotational spectroscopy. J Mol Spectrosc 280:47-3
  14. Stephens SL, Walker NR, Legon AC (2011) Molecular geometries of H₂S?ICF₃ and H₂O?ICF₃ characterised by broadband rotational spectroscopy. Phys Chem Chem Phys 13:21093-1101
  15. Stephens SL, Walker NR, Legon AC (2011) Internal rotation and halogen bonds in CF₃I?NH₃ and CF₃I?N(CH₃)₃ probed by broadband rotational spectroscopy. Phys Chem Chem Phys 13:20736-0744
  16. Ste
• 作者单位：J. Grant Hill (17)
  Anthony C. Legon (18)
  David P. Tew (18)
  Nicholas R. Walker (19)
  
  17. Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK
  18. School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK
  19. School of Chemistry, Bedson Building, Newcastle University, Newcastle-upon-Tyne, NE1 7RU, UK
  
• 丛书名：Halogen Bonding I
• ISBN：978-3-319-14057-5
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Organic Chemistry
  Inorganic Chemistry
  Theoretical and Computational Chemistry
  Medicinal Chemistry
  Biochemistry
  Organometallic Chemistry
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1436-5049

文摘

Methods for observing the rotational spectra of the halogen-bonded complexes B?ICl and B?ICF3 (B-?N2, CO, HC≡CH, H2C=CH2, H2O, H2S, PH3 or NH3) and deriving from them properties such as angular geometry, radial geometry, the strength of the intermolecular bond, and the extent of electron redistribution on complex formation are described. Comparison of various properties reveals several similarities between the two series. Thus, the B?ICF3 obey a set of rules which were originally proposed to rationalise the angular geometries of hydrogen-bonded complexes of the type B?HX, but which were subsequently found to apply to their halogen-bonded analogues B?XY, where XY is a dihalogen molecule, including ICl. Important for establishing the validity of these rules in both series B?ICl and B?ICF3 were the complexes with B-?H2O or H2S. The configuration at O in H2O?ICF3 and H2O?ICl is effectively planar. On the other hand, the configuration at S in H2S?ICF3 and H2S?ICl is permanently pyramidal. Ab initio calculations of potential energy functions for inversion at O or S performed at the CCSD(T)(F12*)/cc-pVDZ-F12 level of theory confirmed these conclusions. Comparison of the intermolecular stretching force constants k σ show that the series B?ICF3 is systematically more weakly bound than B?ICl. Interpretation of k σ in terms of nucleophilicities N B of B and electrophilicities E IR of ICl and ICF3 reveals that \( {E}_{{\mathrm{ICF}}_3}\approx {E}_{\mathrm{ICl}}/3 \) . Experimental and ab initio values of distances r(Z?I), where Z is the acceptor atom/region of B, show that, for a given B, the intermolecular bond of B?ICF3 is longer than that of B?ICl. The electronic charge redistributed from B to ICF3 on formation of B?ICF3 is probably negligibly small.