Structural Studies of a Borane-Modified Phosphate Diester Linkage: Ab Initio Calculations on the Dimethylboranophosphate Anion and the Single-Crystal X-ray Structure of Its Diisopropylammonium Salt

Inorganic Chemistry

Volumn 37, Issue 17, 1998, Pages 4158-4159

  Summers, Jack S ^a   Roe, Diana ^b   Boyle, Paul D ^c   Colvin, Michael ^d   Shaw, Barbara Ramsay ^a  

^a DUKE UNIVERSITY   (United States)

^b SANDIA NATIONAL LABORATORIES   (United States)

^c NORTH CAROLINA STATE UNIVERSITY   (United States)

^d LAWRENCE LIVERMORE NATIONAL LABORATORY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000685245     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic971435z     Document Type: Article

References (25)

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2. (a) Sergueev, D.; Shaw, B. R. Submitted to J. Am. Chem. Soc.
3. (b) Sergueev, D.; Hasan, A.; Ramaswamy, M.; Shaw, B. R. Nucleosides Nucleotides 1997, 16, 1533-8.
4. Shaw, B. R.; Madison, J.; Sood, A.; Speilvogel, B. F. Methods Mol. Biol. 1993 20, 225.
5. Sood, A.; Shaw, B. R.; Speilvogel, B. F. J. Am. Chem. Soc. 1990, 112, 9000-1.
6. Li, H.; Porter, K.; Huang, F.; Shaw, B. R. Nucleic Acids Res. 1995, 23, 4495-501.
7. Li, H.; Hardin, C.; Shaw, B. R. J. Am. Chem. Soc. 1996, 118, 6606-14.
8. 3, was published (without crystallographic parameters) in a report describing some of the chemistry of the anion. Imamoto, T.; Nagato, E.; Wada, Y.; Masuda, K.; Yamaguchi, K.; Uchimaru, T. J. Am. Chem. Soc. 1997, 119, 9925-6.
9. Johnson, C. K. ORTEP - A Fortran Thermal Ellipsoid Plot Program. Technical Report ORNL-5138; Oak Ridge National Laboratory: Oak Ridge, TN, 1976.
10. 1/2), between observed and calculated ADP values was 0.033. For further information, see: Dunitz, J. D.; Schomaker, V.; Trueblood, K. N. J. Phys. Chem. 1988, 92, 856-67.
11. Ab initio calculations were performed using the program Gaussian 94. Each molecular structure was fully optimized with the 6-31+G** basis set using both the MP2 and the Hartree-Fock approximations (Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Kieth, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzeewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, Revision B.1; Gaussian, Inc.: Pittsburgh, PA, 1995). The geometries were also optimized by applying a solvent model, using the self-consistent isodensity variation (SCI-PCM) of the polarized continuum model reaction field, to the HF/ 6-31+G** calculated structures. We also calculated atomic charges for the MP2-optimized gas-phase compounds using a natural bond order basis (as opposed to the atomic orbital basis), a method called natural population analysis (Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899). This method tends to be more reliable than using standard Mulliken populations, but yields somewhat more polar bonds.
12. Ab initio calculations were performed using the program Gaussian 94. Each molecular structure was fully optimized with the 6-31+G** basis set using both the MP2 and the Hartree-Fock approximations (Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Kieth, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzeewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, Revision B.1; Gaussian, Inc.: Pittsburgh, PA, 1995). The geometries were also optimized by applying a solvent model, using the self-consistent isodensity variation (SCI-PCM) of the polarized continuum model reaction field, to the HF/ 6-31+G** calculated structures. We also calculated atomic charges for the MP2-optimized gas-phase compounds using a natural bond order basis (as opposed to the atomic orbital basis), a method called natural population analysis (Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899). This method tends to be more reliable than using standard Mulliken populations, but yields somewhat more polar bonds.
13. Thatcher, G. R. J.; Campbell, A. S. J. Org. Chem. 1993, 58, 2272-81.
14. Positions of the borane hydrogens were obtained from difference Fourier maps, not by optimization as a constrained group.
15. Corbridge, D. E. C. The Structural Chemistry of Phosphorus; Elsevier Scientific Publishing Co.: Amsterdam, 1974.
16. (a) Edmundson, R. S. In The CRC Handbook of Phosphorus-31 NMR Data; Tebby, J. C., Ed.; CRC Press: Boca Raton.
17. (b) Verkade, J. G. Coord. Chem. Rev. 1972/73, 9, 1.
18. (a) Zottola, M. A.; Pedersen, L. G.; Singh, P.; Shaw, B. R. In Modeling the Hydrogen Bond; Smith, D. A., Ed.; ACS Symp. Ser. 567; American Chemical Society: Washington, DC, 1994; p 277-85.
19. (b) Crabtree, R. H.; Siegbahn, P. E. M.; Eisenstein, O.; Rheingold, A. L.; Koetzle, T. F. Acc. Chem. Res. 1996, 29, 348-54.
20. Cramer, C. J.; Gladfelter, W. L. Inorg. Chem. 1997, 36, 5358.
21. Of the five closest contacts to the borane group, four are methyl hydrogen atoms (found 2.974(9), 3.142(6), 3.474(11), and 3.595(6) Å from the boron position) and one is a methine hydrogen (3.20(2) Å from boron).
22. Huang, F. Ph.D. Dissertation, Duke University, 1994.
23. Porter, K. W.; Briley, J. D.; Shaw, B. R. Nucleic Acids Res. 1997, 25, 1611-7.
24. m term, our kinetics studies indicate that the difference is primarily due to a decrease in the rate at which bound substrate is converted into product.
25. 1/2.