Abstract
Bond strengths for a series of Group 15 tetrachloride anions AC1 −4 (A = P, As, Sb, and Bi) have been determined by measuring thresholds for collision-induced dissociation of the anions in a flowing afterglow-tandem mass spectrometer. The central atoms in these systems have ten electrons, which violates the octet rule: the bond dissociation energies for ACl −4 help to clarify the effect of the central atom on hypervalent bond strengths. The 0 K bond energies in kJ mol−1 are D(Cl3A-Cr−1) = 90 ± 7, 115 ± 7, 161 ± 8, and 154 ± 15, respectively. Computational results using the B3LYP/LANL2DZpd level of theory are higher than the experimental bond energies. Calculations give a geometry for BiCl −4 that is essentially tetrahedral rather than the see-saw observed for the other tetrachlorides. NBO calculations predict that the phosphorus and arsenic systems have 3C-4E bonds, while the antimony and bismuth systems are more ionic.
Article PDF
Similar content being viewed by others
References
Reed, A. E.; Schleyer, P. v. R. Chemical Bonding in Hypervalent Molecules. The Dominance of Ionic Bonding and Negative Hyperconjugation Over δ-Orbital Participation. J. Am. Chem. Soc. 1990, 112, 1434–1445.
Norman, N. C. Periodicity and the P-block Elements. Oxford University Press: Oxford, 1994.
Magnusson, E. Hypercoordinate Molecules of Second-Row Elements: d Functions or d Orbitals? J. Am. Chem. Soc. 1990, 112, 7940–7951.
Schaefer, H. F., Ed. Modern Theoretical Chemistry, Vol. 3. Plenum: New York, 1977.
Hach, R. J.; Rundle, R. E. The Structure of Tetramethylammonium Pentaiodide. J. Am. Chem. Soc. 1951, 73, 4321–4324.
Pimentel, G. C. The Bonding of Trihalide and Bifluoride Ions by the Molecular Orbital Method. J. Chem. Phys. 1951, 19, 446–448.
Kaupp, M.; van Wüllen, Ch.; Franke, R.; Schmitz, F.; Kutzelnigg, W. The Structure of XeF6 and of Compounds Isoelectronic with It. A Challenge to Computational Chemistry and to the Qualitative Theory of the Chemical Bond. J. Am. Chem. Soc. 1996, 118, 11939–11950.
Heard, G. L.; Marsden, C. J.; Scuseria, G. E. The Trifluoride Anion: A Difficult Challenge for Quantum Chemistry. J. Phys. Chem. 1992, 96, 4359–4366.
Novoa, J. J.; Mota, F.; Alvarez, S. Structure and Stability of the X3 Systems (X = F, Cl, Br, I) and Their Interaction with Cations. J. Phys. Chem. 1988, 92, 6561–6566.
Landrum, G. A.; Goldberg, N.; Hoffmann, R. Bonding in the Trihalides (X −3 ), Mixed Trihalides (X2Y−) and Hydrogen Bihalides (X2H−). The Connection Between Hypervalent, Electron-rich Three-Center, Donor-Acceptor and Strong Hydrogen Bonding. J. Chem. Soc., Dalton Trans. 1997, 3605–3613.
Gutsev, G. L. Structure and Stability of Trihalogens and Their Anions. Russ. J. Phys. Chem. 1992, 66, 1596–1599.
Cahill, P. A.; Dykstra, C. E.; Martin, J. C. The Structure and the Stability of the 10-F-2 Trifluoride Ion, a Compound of a Hypervalent First Row Element. J. Am. Chem. Soc. 1985, 107, 6359–6362.
Atkins, P. W.; Jones, L. L. Chemistry: Molecules, Matter and Change; 3rd ed. W. H. Freeman: New York, 1997.
Chang, R. Chemistry; 6th ed. McGraw-Hill: Boston, 1998.
McMurry, J.; Fay, R. C. Chemistry; 2nd ed. Prentice-Hall: Upper Saddle River, NJ, 1998.
Ebbing, D. D.; Gammon, S. D. General Chemistry; 6th ed. Houghton Mifflin: Boston, 1999.
Silverberg, M. Chemistry; 2nd ed. McGraw-Hill: Boston, 2000.
Brown, T. L.; LeMay, H. E.; Bursten, B. E. Chemistry: The Central Science; 8th ed. Prentice Hall: Upper Saddle River, NJ, 2000.
Brady, J. E.; Russell, J. W.; Holum, J. R. Chemistry: Matter and Its Changes; 3rd ed. Wiley: New York, 2000.
Zumdahl, S. S.; Zumdahl, S. A. Chemistry; 5th ed. Houghton Mifflin: Boston, 2000.
Häser, M. Characterization of Electronic Structure in Molecules by One-Center Expansion Techniques. No Three-Center Four-Electron Bond in PF5. J. Am. Chem. Soc. 1996, 118, 7311–7325.
Cioslowski, J.; Mixon, S. T. Rigorous Interpretation of Electronic Wave Functions. 2. Electronic Structures of Selected Phosphorus, Sulfur, and Chlorine Fluorides and Oxides. Inorg. Chem. 1993, 32, 3209–3216.
Nizzi, K. E.; Pommerening, C. A.; Sunderlin, L. S. Gas-Phase Thermochemistry of Polyhalide Anions. J. Phys. Chem. A 1998, 102, 7674–7679.
Moc, J.; Morokuma, K. Ab Initio MO Study on the Periodic Trends in Structures and Energies of Hypervalent Compounds: Four-Coordinated XH −4 and XF −4 Anions Containing a Group 15 Central Atom (X= P, As, Sb, Bi). Inorg. Chem. 1994, 33, 551–560.
Gutsev, G. L. A Theoretical Study on the Structure and Stability of the PF n and PF − n Series, n = 1–6. J. Chem. Phys. 1993, 98, 444–452.
Tschumper, G. S.; Fermann, J. T.; Schaefer, H. F., III. Structure, Thermochemistry, and Electron Affinities of the PF n and PF − n Series, n = 1–6. J. Chem. Phys. 1996, 104, 3676–3683.
Gu, J.; Chen, K.; Xie, Y.; Schaefer, H. F., III; Morris, R. A.; Viggiano, A. A. The Electron Affinities of PF and PF2. J. Chem. Phys. 1998, 108, 1050–1054.
Gutsev, G. L. A Theoretical Study on the Structure and Stability of the PCln and PCl −n Series, n = 1–6. Chem. Phys. 1994, 179, 325–339.
Moc, J.; Morokuma, K. Ab Initio Molecular Orbital Study on the Periodic Trends in Structures and Energies of Hypervalent Compounds: Five-Coordinated XH5 Species Containing a Group 15 Central Atom (X = P, As, Sb, and Bi). J. Am. Chem. Soc. 1995, 117, 11790–11797.
Moc, J.; Morokuma, K. Ab Initio MO Study on the Periodic Trends in Structures and Energies of Hypervalent Compounds: Five-, Six-, and Seven-Coordinated XF5, XH −6 , XF −6 , XH 27 and XF 2/−7 Species Containing a Group 15 Central Atom (where X is P, As, Sb, Bi). J. Mol. Struct. 1997, 436-437, 401–418.
Briedung, J.; Thiel, W. A Systematic Ab Initio Study of the Group V Trihalides MX3 and Pentahalides MX5 (M = P- Bi, X = F - I). J. Comp. Chem. 1992, 13, 165–176.
Trinquier, G.; Daudey, J.; Caruana, G.; Madaule, V. Theoretical Data on the Multicoordination of Phosphorus and Arsenic. J. Am. Chem. Soc. 1984, 106, 4794–4799.
Armentrout, P. B.; Kickel, B. L.“Gas-Phase Thermochemistry of Transition metal Ligand Systems: Reassessment of Values and Periodic Trends,” in Organometallic Ion Chemistry, Freiser, B. S. Ed.; Kluwer: Amsterdam, 1996, 1–45. Armentrout, P. B. “Gas-Phase Organometallic Chemistry,” in Topics in Organometallic Chemistry Vol. 4, Brown, J. M.; Hofmann, P. Eds.; Springer-Verlag: Berlin, 1999. More, M. B.; Ray, D.; Armentrout, P. B. Intrinsic Affinities of Alkali Cations for 15-Crown-5 and 18-Crown-6: Bond Dissociation Energies of Gas-Phase M+-Crown Ether Complexes J. Am. Chem. Soc. 1999, 121, 417–423.
Sunderlin, L. S. “Hypervalent Bonding in Gas-Phase Anions,” in Advances in Gas-Phase Ion Chemistry, Vol. 4, Adams, N.; Babcock, L., eds.; JAI Press: Greenwich, CT, 2001.
Larson, J. W.; McMahon, T. B. Strong Hydrogen Bonding in Gas-Phase Anions. An Ion Cyclotron Resonance Determination of Fluoride Binding Energetics to Brønsted Acids from Gas-Phase Fluoride Exchange Equilibria Measurements. J. Am. Chem. Soc. 1983, 150, 2944–2950.
Larsen, J. W.; McMahon, T. B. Fluoride and Chloride Affinities of Main Group Oxides, Fluorides, Oxofluorides, and Alkyls. Quantitative Scales of Lewis Acidities from Ion Cyclotron Resonance Halide-Exchange Equilibria. J. Am. Chem. Soc. 1985, 107, 766–773.
For possible adjustments to the fluoride affinity scale see also Wenthold, P. G.; Squires, R. R. Bond Dissociation Energies of F −2 and HF −2 . A Gas-Phase Experimental and G2 theoretical Study. J. Phys. Chem. 1995, 99, 2002–2005.
Haartz, J. C.; McDaniel, D. H. Fluoride Ion Affinity of Some Lewis Acids. J. Am. Chem. Soc. 1973, 95, 8562–8565.
Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. The Group 15 Elements: P, As, Sb, Bi. In Advanced Inorganic Chemistry; 6th ed. Wiley Interscience: New York, 1999.
Chapman, D. M.; Buchanan, A. C., III; Smith, G. P.; Mamantov, G. Bonded vs. Nonbonded Electron Transfers in Molten Salts: Characterization and Rates of Formation of the Radical Cations and Dications of Phenoxazine and Phenothiazine and Behavior of the M(2, 2′-bipyridine) 3+3/2+ (M = Fe, Ru, Os) Complexes in SbCl3-Rich Media. J. Am. Chem. Soc. 1986, 108, 654–663.
Emsley, J.; Hall, D. The Chemistry of Phosphorus. Harper & Ltd.: London, 1976.
Christe, K. O.; Wilson, W. W.; Boatz, J. A. N +5 : A Novel Homoleptic Polynitrogen Ion as a High Energy Density Material. Angew. Chem. Int. Ed. Engl. 1999, 38, 2004–2009.
McAliffe, C. A.; Levason, W. Studies in Inorganic Chemistry 1: Phosphine, Arsine, Stilbine Complexes of the Transition Elements. Elsevier Scientific Publishing Company: Amsterdam, 1979.
Muntean, F.; Armentrout, P. B. Guided Ion Beam Study of Collision-Induced Dissociation Dynamics: Integral and Differential Cross Sections. J. Chem. Phys. 2001, 115, 1213–1228, and refs. therein.
Ervin, K. M.; Armentrout, P. B. Translational energy dependence of Ar+ + XY 5′76 ArX+ + Y (XY = H2, D2, HD) from thermal to 30 eV c.m.. J. Chem. Phys. 1985, 83, 166–189.
Rodgers, M. T.; Ervin, K. M.; Armentrout, P. B. Statistical Modeling of Collision-Induced Dissociation Thresholds. J. Chem. Phys 1997, 106, 4499–4508.
Do, K.; Klein, T. P.; Pommerening, C. A.; Sunderlin, L. S. A New Flowing Afterglow-Guided Ion Beam Tandem Mass Spectrometer. Applications to the Thermochemistry of Polyiodide Ions. J. Am. Soc. Mass Spectrom. 1997, 8, 688–696.
Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds Part A: Theory and Applications in Inorganic Chemistry; 5th ed. John Wiley & Sons: New York, 1997.
Ahlijah, G. Y.; Goldstein, M. Far-infrared and Raman Spectra of Tetrahalogeno-complexes of Arsenic(III), Antimony(III), and Bismuth(III). J. Chem. Soc. A 1970, 2, 326–330.
Ahlijah, G. Y.; Goldstein, M. Vibrational Spectra of Tetrahalogenocomplexes of Antimony(III) and Bismuth(III). Chem. Comm. 1968, 21, 1356–1358.
Hay, P. J.; Wadt, W. R. Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg. J. Chem. Phys. 1985, 82, 270–283.
Wadt, W. R.; Hay, P. J. Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi. J. Chem. Phys. 1985, 82, 284–298.
Hay, P. J.; Wadt, W. R. Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals. J. Chem. Phys. 1985, 82, 299–310.
Check, C. E.; Faust, T. O.; Bailey, J. M.; Wright, B. J.; Gilbert, T. M.; Sunderlin, L. S. Addition of Polarization and Diffuse Functions to the LANL2DZ Basis Set for P-Block Elements. J. Phys. Chem. A 2001, 105, 8111–8116.
Loh, S. K.; Hales, D. A.; Lian, L.; Armentrout, P. B. Collision-Induced Dissociation of Fen+ (n = 2–10) with Xe: Ionic and Neutral Iron Binding Energies. J. Chem. Phys. 1989, 90, 5466–5485.
Schultz, R. H.; Crellin, K. C.; Armentrout, P. B. Sequential Bond Energies of Fe(CO) +x (x = 1–5): Systematic Effects on Collision-Induced Dissociation Measurements. J. Am. Chem. Soc. 1991, 113, 8590–8601.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, A. D.; Rabuck, K. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.9. Gaussian, Inc.: Pittsburgh, PA, 1998.
Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Bohmann, J. A.; Morales, C. M.; Weinhold, F. Theoretical Chemistry Institute: University of Wisconsin, Madison, WI, 2001NBO 5.0http://www.chem.wisc.edu/~nbo5.
Cioslowski, J.; Mixon, S. T. Rigorous Interpretation of Electronic Wave Functions. 2. Electronic Structures of Selected Phosphorus, Sulfur, and Chlorine Fluorides and Oxides. Inorg. Chem. 1993, 32, 3209–3216.
Bader, R. F. W. Atoms in Molecules: A Quantum Theory. Clarendon Press: Oxford, 1990.
Cioslowski, J.; Nanayakkara, A.; Challacombe, M. Rapid evaluation of atomic properties with mixed analytical/numerical integration. Chem. Phys. Lett. 1993, 203, 137–142.
Cioslowski, J.; Surjan, P. R. An observable-based interpretation of electronic wavefunctions: application to “hypervalent” molecules. J. Mol. Struc. 1992, 255, 9–33.
Cioslowski, J.; Stefanov, B. B. Variational determination of the zeroflux surfaces of atoms in molecules. Mol. Phys. 1995, 84, 707–716.
Stefanov, B. B.; Cioslowski, J. R. An Efficient Approach to Calculation of Zero-Flux Atomic Surfaces and Generation of Atomic Integration Data. J. Comp. Chem. 1995, 16, 1394–1404.
Cioslowski, J. Isopycnic Orbital Transformations and Localization of Natural Orbitals. Int. J. Quant. Chem. Quant. Chem. Symp. 1990, 24, 15–28.
Cioslowski, J.; Mixon, S. T. Covalent Bond Orders in the Topological Theory of Atoms in Molecules. J. Am. Chem. Soc. 1991, 113, 4142–4145.
Cioslowski, J. An Efficient Evaluation of Atomic Properties Using a Vectorized Numerical Integration with Dynamic Thresholding. Chem. Phys. Lett. 1992, 194, 73–78.
Cioslowski, J. A New Robust Algorithm for Fully Automated Determination of Attractor Interaction Lines in Molecules. Chem. Phys. Lett. 1994, 219, 151–154.
Heats of formation for P and Cl from: Afeefy, H. Y.; Liebman, J. F.; Stein, S. E. “Neutral Thermochemical Data” in NIST Chemistry WebBook, NIST Standard Reference Database Number 69, Linstrom, P. J.; Mallard, W. G., Eds., July 2001, National Institute of Standards and Technology, Gaithersburg MD, 20899 (http://webbook.nist.gov). Other data from: Woods, T. L.; Garrels, R. M. Thermodynamic Values at Low Temperatures for Natural Inorganic Materials: An Uncritical Summary. Oxford University Press: Oxford, 1987.
Mingos, D. M. P. Essential Trends in Inorganic Chemistry. Oxford University Press: Oxford, 1998.
Gailbreath, B. D.; Pommerening, C. A.; Bachrach, S. M.; Sunderlin, L. S. Potential Energy Surface of SCl −3 . J. Phys. Chem. A 2000, 104, 2958–2961.
Author information
Authors and Affiliations
Corresponding author
Additional information
This paper is dedicated to Peter Armentrout in celebration of his winning the 2001 Biemann Medal, and in appreciation of his mentoring and friendship.
Rights and permissions
About this article
Cite this article
Walker, B.W., Check, C.E., Lobring, K.C. et al. The thermochemistry of group 15 tetrachloride anions. J Am Soc Mass Spectrom 13, 469–476 (2002). https://doi.org/10.1016/S1044-0305(02)00369-0
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/S1044-0305(02)00369-0