Brian J. Frost
Inorganic and Organometallic Chemistry; Catalysis
B.S. (1995), Elizabethtown College; Ph.D. (1999), Texas A&M University (Donald J. Darensbourg); Postdoctoral Research Associate (2000-2002), Columbia University (Jack R. Norton).
Office: CB 121
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Brian J. Frost
The Frost group is interested in the development of new inorganic and organometallic complexes for use in aqueous and biphasic catalysis. Organometallic chemistry and catalysis remain exciting areas of research with many opportunities for fundamental, not to mention pedagogical, contributions. We are interested in the synthesis, structure, and reactivity of inorganic and organometallic complexes with emphasis on those applicable to catalysis. Techniques utilized in our laboratory include, but are not limited to, computational chemistry, multinuclear NMR spectroscopy (1H, 13C, 31P), UV-vis spectroscopy, mass specrometry, X-ray crystallography, and in situ IR using ASI's ReactIR 4000.TM
Our research program encompasses a wide range of interests including:
- Green chemistry
- Coordination chemistry
- Catalysis in aqueous, organic, and biphasic media
- Kinetic and mechanistic studies of catalytic processes
- Small molecule activation
- Ligand synthesis (organic synthesis)
Currently our group is working on projects involving the synthesis and characterization of new water-soluble phosphines and exploring the catalytic activity of the inorganic and organometallic complexes derived from these new ligands. Many of the phosphine ligands we synthesize are derived from the water-soluble and air-stable phosphine PTA (see figure). For example, deprotonation of the upper-rim of PTA with n-BuLi has allowed for access to a variety of chiral water-soluble phosphine ligands (see figure).
Aqueous phase catalysis has a number of advantages over traditional organic phase homogeneous catalysis; the most widely recognized is the use of, the environmentally benign solvent, water as the reaction medium. Water-soluble catalysts may be easily separated, recovered, and reused through the use of biphasic catalysis or extraction of the organic product from the aqueous layer. We have recently shown that RuCl2PTA4 is an excellent catalyst for the aqueous phase hydration of a variety of nitriles to amides. The reaction conditions are reasonably mild and the catalyst is robust enough to be recycled more than seven times with little loss of activity. In a number of cases the aqueous layer could be decanted away from the crystalline product and reused without a column or extraction (see Green Chem. 2012, 14, 62-66).
Lee, W.-C.; Frost, B.J. Aqueous and biphasic nitrile hydration catalyzed by a recyclable Ru(II) complex under atmospheric conditions. Green Chem. 2012, 14, 62-66.
Nair, R.P.; Pineda-Lanorio, J.A.; Frost, B.J. Atom transfer radical addition (ATRA) of carbon tetrachloride and chlorinated esters to various olefins catalyzed by Cp'Ru(PPh3)(PR3)Cl complexes. Inorg. Chim. Acta 2012, 380, 96-103. [Invited contribution for the "Young Investigator Award Special Issue"]
Weeden, J.A.; Huang, R.; Galloway, K.D.; Gingrich, P.W.; Frost, B.J. The Suzuki Reaction in Aqueous Media Promoted by P, N Ligands. Molecules 2011, 16, 6215-6231.
Frost, B. J.; Lee, W.-C.; Pal, K.; Kim, T. H.; VanDerveer, D.; Rabinovich, D. Synthesis, Structure, and Coordination Chemistry of O=PTA and S=PTA with Group 12 Metals (PTA = 1,3,5-triaza-7-phosphaadamantane). Polyhedron 2010, 29, 2373-2380.
Nair, R. P.; Kim, T.; Frost, B. J. Atom Transfer Radical Addition Reactions of CCl4, CHCl3, and p-Tosyl Chloride Catalyzed by Cp'Ru(PPh3)(PR3)Cl Complexes. Organometallics 2009, 28, 4681-4688.
Wong, G.W.; Lee, W.-C.; Frost, B.J. Insertion of CO2, ketones, and aldehydes into the C-Li bond of 1,3,5-triaza-7-phosphaadamantan-6-yllithium. Inorg. Chem. 2008, 47, 612-620.
Huang, R.; Frost, B.J. Development of a series of P(CH2N=CHR)3 and trisubstituted 1,3,5-triaza-7-phosphaadamantane ligands. Inorg. Chem. 2007, 46, 10962-10964.
Mebi, C.A.; Frost, B.J. Isomerization of trans-[Ru(PTA)4Cl2] to cis-[Ru(PTA)4Cl2] in water and organic solvent: Revisiting the chemistry of [Ru(PTA)4Cl2]. Inorg. Chem. 2007, 46, 7115-7120.
Mebi, C.A.; Nair, R.P.; Frost, B.J. pH dependent selective transfer hydrogenation of α,β-unsaturated carbonyls in aqueous media utilizing half-sandwich ruthenium (II) complexes. Organometallics 2007, 26, 429-438.
Wong, G.W.; Harkreader, J.L.; Mebi, C.A.; Frost, B.J. Synthesis and coordination chemistry of a novel bidentate phosphine, 6-(diphenylphosphino)-1,3,5-triaza-7-phosphaadamantane (PTA-PPh2). Inorg. Chem. 2006, 45, 6748-6755.
Frost, B.J.; Bautista, C.M.; Huang, R.; Shearer, J. Manganese complexes of 1,3,5-triaza-7-phosphaadamantane (PTA): The first nitrogen bound transition metal complex of PTA. Inorg. Chem. 2006, 45, 3481-3483. (Communication)
Frost, B.J.; Mebi, C.A.; Gingrich, P.W. Boron-nitrogen adducts of 1,3,5-triaza-7-phosphaadamantane (PTA): Synthesis, reactivity, and molecular structure. Eur. J. Inorg. Chem. 2006, 1182-1189.
Mebi, C.A.; Frost, B.J. Effect of pH on the biphasic catalytic hydrogenation of benzylidene acetone using CpRu(PTA)2H. Organometallics 2005, 24, 2339-2346.