Organosilicon and Main Group Chemistry

Our research spans the interface between inorganic and organic chemistry. We have a special interest in organometallic compounds of the main group in which metal atoms play important roles in determining structure and reactivity. One approach we have utilized in recent years has been to replace key carbon atoms in organic structures with silicon (e.g., 1-silacyclopentadienide, 1-silacyclopropane, 1-silaadamantane) and study the mechanisms of substitution reactions at the silicon centers. These investigations, which provide sharp contrasts between carbon and silicon chemistry, not only give us the basic information we need to understand the chemistry of organosilanes but also offer a useful framework for developing approaches to the study of other organometallic compounds.

Catalysis of organometallic reactions is far less common than the catalysis of organic reactions. We develop new reagents for the catalysis of hydrosilylation reactions with an emphasis on conjugated olefins and functionalized silanes as the substrates. Also under study is the catalytic dehydrogenative coupling of hydrosilanes to produce poly silanes. We are particularly interested in polymers containing metal atoms. Homogeneous and hetero geneous catalysts as well as ultrasonic activation of catalytic processes are being studied.

New routes to semiconductors and other important inorganic materials via gentle pyrolysis of organometallic compounds is a new area of research for our group. By relatively simple methods using novel mechanisms not common in the field of organometallic chemical vapor deposition (OMCVD) we have efficiently prepared binary and ternary materials of Groups 13-15 and 14-16 of high purity. By our new procedures we synthesize novel non-stoichiometric materials such as SnS0.8Se0.2 and other SnSxSe1-x combinations under very mild conditions from readily prepared organometallic compounds.

Selected Publications

"XRD and SEM Characterization of Compound Semiconductor Solid Solutions: (Sn(S,Se) and (Pb,Cd)S" B. R. Jarabek, D. G. Grier, D. L. Simonson, D. J. Seidler, P. Boudjouk and G. J. McCarthy, Advances in X-Ray Analysis, Vol. 40, 710-718, 1998; CD-ROM.

"Dichloro(N,N,N'N'-tetraethyl-1,2-ethane-N,N')silicon"", S. D. Kloos and P. Boudjouk, Inorganic Syntheses, Vol. 32, pp 294-297, M. Y. Darensbourg, Ed., Wiley-Inter-science, New York, NY., 1998.

"An Unexpected Redistribution of Trichlorosilane. Synthesis, Structure and Bonding of (teeda)Dichlorosilane", P. Boudjouk, B.-K. Kim, S. D. Kloos, M. Page and D. Thweatt, J. Chem. Soc. Dalton, 877-880, 1998.

"Nickel Catalyzed Silane Reductions of a, b - Unsaturated Ketones and Nitriles", P. Boudjouk, S.-B. Choi, B. J. Hauck, and A. B. Rajkumar, Tetrahedron. Lett., 39, 3951-3952, 1998.

"Aromatic Benzannulated Silole Dianions. The Dilithio and Disodio Salts of a Silaindenyl Dianion", S.-K. Choi and P. Boudjouk, and P. Wei, J. Am. Chem. Soc., 120, 5814-5815, 1998.

"Tris(benzylthiolato)bismuth. Efficient Precursor to Phase Pure Polycrystalline Bi2S3" P. Boudjouk, M. P. Remington, D. G. Grier, B. R. Jarabek, and G. J. McCarthy, Inorg. Chem., 37, 3538-3541, 1998.

"Metal Bis(benzylthiolates): Efficient Single Source Precursors to Solid Solutions and Nanoparticles of Metal Sulfides", P. Boudjouk, B. R. Jarabek, D. L. Simonson, D. J. Seidler, D. G. Grier, G. J. McCarthy, and L. P. Keller, Chem. Mater., 10, 2358-2364, 1998.

"Growth of Antimony Thin Films Using Perbenzylated Organometallic Precursors", M.P. Remington, Jr., S. Kamepalli, P. Boudjouk, B. R. Jarabek, D. G. Grier, R. S. Winburn, B. E. Very, G. J. McCarthy, Mater. Res. Soc. Proc. 547, 481-484, 1999.

"New Neutral Carrier-type Ion Sensors. Crown Ether Derivatives of Poly(methylhydro-siloxane)", B. P. S. Chauhan and P. Boudjouk, Tetrahedron Lett., 40, 4123-4126, 1999.

"A New Catalyst for Exclusive ß-Hydrosilylation of Acrylonitrile", M. Chauhan and P. Boudjouk, Tetrahedron Lett., 40, 4127-4128, 1999.

"Unique Bis-h5, h1 Bonding in a Dianionic Germole. Synthesis and Structural Characterization of the Dilithium Salt of the 2,3,4,5-Tetraethyl Germole Dianion", S.-B. Choi, P. Boudjouk, and J.-H. Hong, Organometallics, 18, 2919-2920, 1999.

"Mechanistic Studies of the Reaction of Hydrosiloles with Nucleophiles. Crystal Structures of the Enantiomers of 1-Methyl-2-dimethylsilyl-2,3,4,5-tetraphenyl-1-sila-cyclo-3-pentene and 1-Bis(trimethylsilyl)amino-5-methyl-2,3,4,5-tetraphenyl-1-silacyclo-3-pentene", S.-B. Choi, P. Boudjouk, and Y. Pan, Organometallics, 18, 3813-3817, 1999.

"New Organosilicon Polymer for the Extraction and Phosphorescence Analysis of Uranyl in Environmental Samples", A. F. Arruda, A. D. Campiglia, B. P. S. Chauhan, and P. Boudjouk, Anal. Chim. Acta, 396, 263-272, 1999.

"2,2,4,4,6,6-Hexabenzylcyclotristannatellurane, (Bn2SnTe)3. Synthesis and Structural Characterization of an Organometallic Single Source Precursor to Phase Pure, Polycrystalline SnTe", P. Boudjouk, M. P. Remington, Jr., D. G. Grier, W. Triebold, and B. R. Jarabek, Organometallics, 18, 4534-4537, 1999.

"Low Temperature Co-Pyrolysis of Hexabenzylditinsulfide and Selenium. An Alternate Route to Sn(SxSe1-x)", P. Boudjouk, M. P. Remington, Jr., D. J. Seidler, B. R. Jarabek, D. G. Grier, B. E. Very, R. L. Jarabek and G. J. McCarthy, Mat. Res. Bull.,34, 2327-2332, 1999

"Synthesis and Characterization of New Cationic Hexacoordinated Silanes", B. -K. Kim, S. D. Kloos, S. -B. Choi, and P. Boudjouk, Inorg. Chem., 39, 728-731, 2000.

"A Novel a-w Silyl Dianionic Salt. The Synthesis and Characterization of Remotely Connected Benzannulated Silole Monoanions", S.-B. Choi and P. Boudjouk, J. Chem. Soc., Dalton Trans, 841-844, 2000.

"An Efficient Pd-Catalyzed Route to Silyl Esters" M. Chauhan, B. P. S. Chauhan and P. Boudjouk, Org. Lett., 2, 1027-1029, 2000.

"Dehydrogenative Condensation of SiH and SH Bonds. A Metal-catalyzed Protocol to Stable Thiopolysiloxanes" B. P. S. Chauhan, P. Boudjouk, Tetrahedron Lett., 41, 1127-30, 2000.

"Aromatic Benzannulated Germole Dianions. The Dilithio and Disodio Salts of a Germaindenyl Dianion", S. K. Choi, P. Boudjouk and K. Qin. Organometallics. 19, 1806-1809, 2000.

"Synthesis and Characterization of Dibenzannulated Silole Dianions. The Dilithio and Disodio Salts of Silafluorenyl Dianions", S.-B. Choi and P. Boudjouk, Tetrahedron Lett., In press.

"Facile and Efficient Synthesis of Siloxane Based Polyamines", T. E. Ready, B. P. S. Chauhan and P. Boudjouk, Macromolecules, Macromolecular Rapid Commun., in press

"A Catalytic Route to GraftedSilicones", B. P. S. Chauhan, T. E. Ready, Z. Al-Badri and P. Boudjouk, Organometallics, in press.

"Reduction of Conjugate Double Bonds with Trichlorosilane", M. Chauhan and P. Boudjouk, Can. J. Chem. [Issue Dedicated to Adrian Brook], in press.