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Biographical Sketch
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Golam Rasul - Research Associate Professor
Department of Chemistry
University of Southern California
University Park
Los Angeles, CA 90089-1661
Place of Birth & Date
Bangladesh, January 31, 1960
Education
B. Sc. University of Dhaka, Bangladesh, 1983
M. Sc. University of Dhaka, Bangladesh, 1985
M. S. University of Massachusetts, North Dartmouth, 1989
Ph. D. University of Southern California, California, 1992
Employment:
Post-Doctoral Fellowship, University of Southern California 1993-94
Senior Research Associate, University of Southern California 1995-96
Research Assistant Professor, University of Southern California 1997-2003
Research Associate Professor, University of Southern California 2003-present
Area of Specialization:
Combined Application of Theory and Experiment in Structural-Mechanistic Studies
Awards and Honors: The Best Graduate Teaching Assistant Award, Department of Chemistry, University of Massachusetts at N. Dartmouth, N. Dartmouth, MA, 1989; Outstanding Academic Achievement Award, Office of International Students and Scholars, University of Southern California, Los Angeles, CA, 1992.
Publications
More than 120 publications in refereed Journals
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Education
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 B.S. (Honorary) Chemistry, University of Dhaka, Bangladesh, 7/1983
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M.S. (Honorary) Organic Chemistry, University of Dhaka, Bangladesh, 7/1985
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M.S. Theoretical Chemistry, University of Massachusetts at Dartmouth, 5/1989
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Ph.D. Physical Organic and Computational Chemistry, University of Southern California, 8/1992
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Postdoctoral Training
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Post-doctoral fellow, University of Southern California, 1993-1994
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Post-doctoral fellow, University of Southern California, 1992-1993
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Academic Appointment, Affiliation, and Employment History
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Non-Tenure Track Appointments
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Research Associate Professor, University of Southern California, 03/01/2003-
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Research Assistant Professor, University of Southern California, 02/01/1997-02/28/2003
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PostDoctoral Appointments
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Senior Research Associate, University of Southern California, 01/01/1995-01/31/1997
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Description of Research
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Summary Statement of Research Interests
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Combined application of theory and experiment in structural-mechanistic studies. Computational study of the higher coordinate main group hydrido cations. Such studies are very useful in identifying new and exciting hypercoordinate carbonium, boronium, alonium, sulfonium and ammonium ions. The real significance of these ions is that they led to the realization of electrophilic substitution and related transformations of saturated hydrocarbons (alkanes) and in general of electrophilic activation of C-H and C-C single bonds. Investigation of possible role of onium dications (superelectrophiles) in superacid catalyzed reactions. Some electrophiles, such as carboxonium ions, nitronium ion and related systems which are capable of further interaction with Bronsted or Lewis superacids can be greatly activated in superacidic systems. These further interactions produce superelectrophiles, which are highly reactive, energetic, high lying intermediates of dipositive nature. They are the de facto reactive intermediates of many electrophilic reactions in superacidic systems.
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Research Keywords
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Computational Chemistry, Superelectrophilic Activation, Carbocation, Carbodication, Onium Ion, Onium Dication
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Research Specialties
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Experimental and ab initio/DFT/IGLO/GIAO-MP2 studies of electron deficient intermediates such as carbocations, carboxonium ions, halonium ions and oxonium ions and superelectrophiles.
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Detailed Statement of Research Interests
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One of the most impressive accomplishment in organic chemistry is the direct observation of reactive electron deficient carbocation intermediates in superacid solutions by Olah in the early sixties. This finding contributed tremendously to the fundamental understanding of organic chemistry. Since the beginning of this era, NMR has been the most powerful and widely used experimental method to gain insight into the structures of, and rearrangement process in the ions. 13C NMR spectroscopy seems to be most suitable method available in exploring the effects of charge delocalization, bond hybridization and substituents on the nature of carbocations.
In recent years, ab initio and density functional theory (DFT) calculational methods have also made significant contributions to the field. This is exemplified by the accurate prediction of structures and thermodynamic properties as well as the direct prediction of NMR chemical shifts by high level theoretical methods. The combined use of both experiment and theory to delineate complex structures of electron deficient intermediates gives further impetus in correlating structure-property relationships of these reactive intermediates in organic reactions. The work of my group is centered with the generation and investigation of electron deficient carbocations, carbodications and onium ions and dications by NMR spectroscopy and various theoretical methods (i.e ab initio, DFT, IGLO (individual gauge for localized orbitals) and GIAO (gauge invariant atomic orbitals) methods). This include the structures of some of the most important carbocation intermediates, effects of heteroatoms on the stability of carbocations and their role in the electrophilic substitution reactions.
We are also engaged in the computational study of the higher coordinate main group hydriodo cations. Such studies are very useful in identifying new and exciting hypercoordinate carbonium, boronium, alonium, sulfonium and ammonium ions. The real significance of these ions is that they led to the realization of electrophilic substitution and related transformations of saturated hydrocarbons (alkanes) and in general of electrophilic activation of C-H and C-C single bonds. CH5+ is considered the parent of nonclassical carbocations containing a five coordinate carbon atom. The cation preferred a Cs symmetrical structure with a three-center two-electron (3c-2e) bond as originally suggested by Olah et al in 1969. Olah also showed that the parent six coordinate carbocation, diprotonated methane (CH62+), has two 3c-2e bonding interactions in its minimum-energy structure. We later showed that even the parent seven coordinate carbocation, triprotonated methane (CH73+) is an energy minimum and has three 3c-2e bonding interactions in its minimum-energy structure. These results indicate the general importance of 3c-2e interactions in protonated alkanes. Schmidbaur and his associates have prepared a variety of highly interesting higher coordinate boron, carbon, nitrogen, oxygen, phosphorus and sulfur gold complexes and determined their X-ray structures.
In future continued research of organic cations and their further activation (superelectrophilic activation) in superacid solutions will be carried out. This includes the preparation, structural characterization, reactivity and theoretical study of onium and carboxonium ions and dications. Continued theoretical and experimental research will also be carried out on new carbocations and carbodications. Superelectrophilic activation of various onium ions will be investigated by CH3/CD3 exchange, hydrogen/deuterium exchange and by calculations. Attempts will be made to generate and study by NMR spectroscopy persistent mono-, di- and trimethylated species of guanidine, urea and thiourea in CH3F:SbF5/SO2ClF solutions. A number of higher coordinate main group hydriodo onium cations (such as BH6+, AlH6+ and related ions) will be studied by various theoretical methods. These ions will also be characterized in superacids by NMR spectroscopy. In continued study of carbocations such as elusive ions as the parent allyl, benzyl, cyclohexyl and phenyl cation will be probed by new preparation techniques under long lived stable ion conditions.
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Publications
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Book Chapter
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Reddy, V. P., Rasul, G.
(2007).
Conformational Studies of Cyclobutylmethyl Carbocations. pp. 106. Washington: Conformational Studies of Cyclobutylmethyl Cations/American Chemical Society Press.
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Journal Article
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Rasul, G., Prakash, G. S., Olah, G. A.
(2007).
Ab Initio/GIAO-CCSD(T) Study of the Effects of Protonation on Borane-Ammonia (H3BNH3) and Related Complexes. J. Mol. Struc.-THEOCHEM.
Vol. 818, pp. 65.
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Rasul, G., Olah, G. A., Prakash, G. S., Linares-Palomino, P. J., Chako, S., Glinton, K., Mathew, T.
(2007).
Friedel–Crafts Alkylations of Arenes with Mono- and Bis(trifluoro-methyl)oxiranes in Superacid Medium: Facile Synthesis of a-(Trifluoro-methyl)- and a,a-Bis(Trifluoromethyl)-ß-Arylethanols. SYNLETT.
Vol. 7, pp. 1158.
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Reddy, V. P., Rasul, G., Prakash, G. S., Olah, G. A.
(2007).
Structural Studies of Nonclassical Cyclobutylmethyl Cations by the ab initio Method. J. Org. Chem..
Vol. 72, pp. 3076.
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Rasul, G., Prakash, G. S., Olah, G. A.
(2006).
" Ab Initio/GIAO-CCSD(T) Study of Propenoyl (H2C=CH-CO+) and Isopentenoyl ((CH3)2C=CH-CO+) Cations and their Superelectrophilic Protonated Dications. J. Phys. Chem. A.
Vol. 110, pp. 1042.
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Rasul, G.
(2006).
Comparative Study of the Hypercoordinate ions C7H9+ and C8H9+ by the Ab Initio/GIAO-CCSD(T) Method. J. Phys. Chem/NA.
Vol. 110, pp. 11320.
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Rasul, G.
(2006).
BF3‚2CF3CH2OH (BF3‚2TFE), an Efficient Superacidic Catalyst for Some Organic Synthetic Transformations. J. Org. Chem/NA.
Vol. 71, pp. 3952.
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Rasul, G.
(2006).
Facile Synthesis of TMS-Protected Trifluoromethylated Alcohols Using Trifluoromethyltrimethylsilane (TMSCF3) and Various Nucleophilic Catalysts in DMF. J. Org. Chem/NA.
Vol. 71, pp. 6806.
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Rasul, G., Olah, G. A., Prakash, G. S.
(2006).
Ab Initio/GIAO-CCSD(T) Study of Bicyclic and Related Strained Olefins. Structures and 13C NMR Chemical Shifts. J. Phys. Chem. A.
Vol. 110, pp. 7197.
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Koltunov, K. Y., Prakash, G. S., Rasul, G., Olah, G. A.
(2006).
Superacidic Activation of Maleimide and Phthalimide and their Reactions with Cyclohexane and Arenes. Eur. J. Org. Chem.. pp. 4861.
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Honors and Awards
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Excellence in Hydrocarbon Research Award, 1998-1999
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Outstanding Academic Achievement Award, 1992-1993
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The Best Graduate Teaching Assistant Award, 1989-1990
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