Contact
Faculty Assistant

Jon Darmon
Coordinating Editor and Lab Manager
jdarmon@princeton.edu
Frick Laboratory, 289
609-258-4883

Research Focus


Brad Carrow video interview

We are interested in the design of transition metal catalysts that can enable broadly applicable organic transformations and address challenges in sustainability and materials chemistry. Our approach is interdisciplinary, bridging the fields of organometallic, physical organic, synthetic organic, and polymer chemistry. One recent area of emphasis in our group is a mechanism-driven approach to the design of ligands and metal complexes that access long-lived, coordinatively unsaturated organometallic species with low valence electron counts, which are understood to be exceptionally reactive but classically have only been accessible as transient intermediates. 

An emerging theme from our efforts has been metal-ligand interactions based on seemingly weak through-space or secondary coordination sphere interactions that nevertheless can be correlated to pronounced catalytic consequences. We have leveraged these effects over the past few years into solutions for challenging non-directed C−H functionalization reactions, carbon-carbon and carbon-heteroatom cross-coupling reactions that operate without the historical requirement of a strong base for sensitive applications, and syntheses of advanced polymers that might enable new concepts for recycling that are currently out of reach using today’s plastics. 

 

Research Areas
Catalysis / Synthesis
Inorganic Chemistry
Honors
  • NIH MIRA Award (2018)
  • NSF CAREER Award (2017)
  • Thieme Chemistry Journal Award (2017)
  • Japan Society for the Promotion of Science (JSPS) Global COE Fellowship (2011)
Selected Recent Publications

McAlpine, N.J.; Wang, L.; Carrow, B.P. "A Diverted Aerobic Heck Reaction Enables Selective 1,3-Diene and 1,3,5-Triene Synthesis through C–C Bond Scission" J. Am. Chem. Soc. 2018, 140, 13634–13639.

Zhang, W.; Waddell, P.M.; Tiedemann, M.A.; Padilla, C.E.; Mei, J.; Chen, L.; Carrow, B.P. “Electron-Rich Metal Cations Enable Synthesis of High Molecular Weight, Linear Functional Polyethylenes” J. Am. Chem. Soc. 2018, 140, 8841–8850.

Chen, L.; Francis, H.; Carrow, B.P. "An 'On-Cycle' Precatalyst Enables Room-Temperature Polyfluoroarylation Using Sensitive Boronic Acids" ACS Catal. 2018, 8, 2989–2994.

Mitsushige, Y.; Yasuda, H.; Carrow, B.P.; Ito, S.; Kobayashi, M.; Tayano, T.; Watanabe, Y.; Okuno, Y.; Hayashi, S.; Kuroda, J.; Okumura, Y.; Nozaki, K. “Methylene-Bridged Bisphosphine Monoxide Ligands for Palladium-Catalyzed Copolymerization of Ethylene and Polar Monomers” ACS Macro Lett. 2018, 7, 305-311.

Chen, L.; Sanchez, D.R.; Zhang, B.; Carrow, B.P. “’Cationic’ Suzuki–Miyaura Coupling with Acutely Base-Sensitive Boronic Acids”J. Am. Chem. Soc. 2017, 139, 12418-12421.

Gorsline, B.J.; Wang, L.: Ren, P.; Carrow, B.P. “C–H Alkenylation of Heteroarenes: Mechanism, Rate, and Selectivity Changes Enabled by Thioether Ligands” J. Am. Chem. Soc. 2017, 139, 9605-9614.

Chen, L.; Ren, P.; Carrow, B.P. “Tri(1-​adamantyl)​phosphine: Expanding the Boundary of Electron-​Releasing Character Available to Organophosphorus Compounds” J. Am. Chem. Soc. 2016, 138, 6392-6395.

Mitsushige, Y.; Carrow B.P.; Ito, S.; Nozaki, K. “Ligand-Controlled Insertion Regioselectivity Accelerates Copolymerization of Ethylene with Methyl Acrylate by Cationic Bisphosphine Monoxide–Palladium Catalysts” Chem. Sci. 2016, 7, 737-744.

Carrow, B.P.; Nozaki, K. “Transition-Metal-Catalyzed Functional Polyolefin Synthesis: Effecting Control through Chelating Ancillary Ligand Design and Mechanistic Insights” Macromolecules 2014, 47, 2541-2455.