Organometallic Catalysis

Since low-coordinate transition metal complexes have unusual geometries, we aim to learn whether this influences the reaction mechanisms of their organometallic reactions. We have studied the first-row metals iron, cobalt, and nickel with the goal of learning how to transform organic molecules with inexpensive metals rather than the precious metals that are most common in catalysis.

We started working in this area by studying organometallic compounds with unpaired electrons (“high-spin”), especially ones in which the metal shares 14 or fewer valence electrons rather than the usual 18. Our research showed that these organometallic complexes are very useful for synthesis and catalysis.

One important organometallic transformation involving these organometallic complexes is beta-hydride elimination. Using both experimental and computational methods, we learned that spin-state changes may be important when first-row metal compounds undergo beta-hydride elimination.

We then applied this fundamental knowledge to catalytic reactions. For example, our cobalt catalysts can perform regioselective and stereoselective isomerization, and add silicon groups to alkenes (hydrosilylation).

In a newer direction, we are currently studying alkene hydrofunctionalizations that use iron and cobalt hydrides to generate radical intermediates. Even though free radicals are reactive, they are stable to water and many other functional groups which makes them very useful in synthesis. Our expertise in metal chemistry has helped us to gain insight into the interesting mechanisms of these reactions.

Current funding: National Institutes of Health, R01 GM129081, “Mechanistically guided improvement in radical alkene coupling by base metal catalysts.”

Relevant Publications

Juan M. I. Serviano, Erik J. T. Phipps, Patrick L. Holland
Intermolecular Hydroalkoxylation and Hydrocarboxylation of 2-Azadienes with High Efficiency
J. Org. Chem.  202388, in press.  
Conner V. Wilson, Dongyoung Kim, Ajay Sharma, Reagan X. Hooper, Rinaldo Poli, Brian M. Hoffman, Patrick L. Holland
Cobalt-Carbon Bonding in a Salen-Supported Cobalt(IV) Alkyl Complex Postulated in Oxidative MHAT Catalysis
J. Am. Chem. Soc.  2022144, 10361-10367.  
Daniel Kim, Guy Pillon, Daniel J. DiPrimio, Patrick L. Holland
Highly Z-Selective Double Bond Transposition in Simple Alkenes and Allylarenes Through A Spin-Accelerated Allyl Mechanism
J. Am. Chem. Soc.  2021143, 3070–3074.  
Sophia L. Shevick, Conner V. Wilson, Simona Kotesova, Dongyoung Kim, Patrick L. Holland, and Ryan Shenvi
Catalytic hydrogen atom transfer to alkenes: a roadmap for metal hydrides and radicals
Chem. Sci.  202011, 12386-12400.  Tenth anniversary issue
Daniel Kim, Chi Chen, Brandon Q. Mercado, Daniel J. Weix, Patrick L. Holland
Mechanistic Study of Alkene Hydrosilylation Catalyzed by a β-Dialdiminate Cobalt(I) Complex    
Organometallics  202039, 2415-2424.  
Dongyoung Kim, S. M. Wahidur Rahaman, Brandon Q. Mercado, Rinaldo Poli, Patrick L. Holland
Roles of Iron Complexes in Catalytic Radical Alkene Cross-Coupling: A Computational and Mechanistic Study
J. Am. Chem. Soc.  2019141, 7473-7485.  (Highlight in Science)
Lisa Roy, Malik H. Al-Afyouni, Daniel E. DeRosha, Bhaskar Mondal, Ida M. DiMucci, Kyle M. Lancaster, Jason Shearer, Eckhard Bill, William W. Brennessel, Frank Neese, Shengfa Ye, Patrick L. Holland
Reduction of CO2 by a Masked Two-Coordinate Cobalt(I) Complex and Characterization of a Proposed Oxodicobalt(II) Intermediate
Chem. Sci.  201910, 918-929.  
Elitsour Rozen, Yaron Erlich, Megan E. Reesbeck, Patrick L. Holland, Chaim N. Sukenik
Functionalized Self-Assembled Monolayers Bearing Diiminate Complexes Immobilized through Covalently Anchored Ligands  
Langmuir  201834, 13472-13480.  
Julian C. Lo, Dongyoung Kim, Chung-Mao Pan, Jacob T. Edwards, Yuki Yabe, Jinghan Gui, Tian Qin, Sara Gutiérrez, Jessica Giacoboni, Myles W. Smith, Patrick L. Holland, Phil S. Baran
Fe-Catalyzed C-C Bond Construction from Olefins via Radicals
J. Am. Chem. Soc.  2017139, 2484-2503.  
K. Cory MacLeod, Richard A. Lewis, Daniel E. DeRosha, Brandon Q. Mercado, Patrick L. Holland
C-H and C-N Activation at Redox-Active Pyridine Complexes of Iron
Angew. Chem. Int. Ed.  201756, 1069-1072.  
Chi Chen, Maxwell Hecht, Aydin Kavara, William W. Brennessel, Brandon Q. Mercado, Daniel J. Weix, Patrick L. Holland
Rapid, Regioconvergent, Solvent-Free Alkene Hydrosilylation with a Cobalt Catalyst
J. Am. Chem. Soc.  2015137, 13244-13247.  
Patrick L. Holland
Distinctive Reaction Pathways at Base Metals in High-Spin Organometallic Catalysts
Acc. Chem. Res.  201548, 1696-1702.  
John A. Gladysz, et al.
Organometallics Roundtable 2013-2014
Organometallics  201433, 1505-1527.  
Thomas R. Dugan, Eckhard Bill, K. Cory MacLeod, William W. Brennessel, Patrick L. Holland
Synthesis, Spectroscopy and Hydrogen/Deuterium Exchange in High-Spin Iron(II) Hydride Complexes
Inorg. Chem.  201453, 2370-2380.  
Chi Chen, Thomas R. Dugan, William W. Brennessel, Daniel J. Weix, Patrick L. Holland
Z-Selective Alkene Isomerization by High-Spin Cobalt(II) Complexes  
J. Am. Chem. Soc.  2014136, 945-955.  (Coverage in Org. Chem. Highlights)
Sarina M. Bellows, Thomas R. Cundari, Patrick L. Holland
Spin Crossover during β-Hydride Elimination in High-Spin Iron(II)- and Cobalt(II)-Alkyl Complexes  
Organometallics   201332, 4741-4751.  (Part of Virtual Issue Honoring Robert Bergman’s 2017 Wolf Prize in Chemistry)
Brian L. Edelbach, Blaze M. Pharoah, Sarina M. Bellows, Peter R. Thayer, Charles N. Fennie, Ryan E. Cowley, Patrick L. Holland
An Expedient Synthesis of 2,4,6-Tris(trifluoromethyl)aniline
Synthesis  201244, 3595-3597.  
Thomas R. Dugan, Jonathan M. Goldberg, William W. Brennessel, Patrick L. Holland
Low-Coordinate Cobalt Fluoride Complexes: Synthesis, Reactions, and Production from C-F Activation Reactions
Organometallics  201231, 1349-1360.  
Barbara A. Reisner, Joanne L. Stewart, B. Scott Williams, Laurel A. Goj, Patrick L. Holland, Hilary J. Eppley, and Adam R. Johnson
Virtual Inorganic Pedagogical Electronic Resource Learning Objects in Organometallic Chemistry
J. Chem. Educ.   201289, 185-187.  
Benjamin R. Dible, Ryan E. Cowley, Patrick L. Holland
Remote Substitution on N-Heterocyclic Carbenes Heightens the Catalytic Reactivity of Their Palladium Complexes
Organometallics   201130, 5123-5132.  
Keying Ding, Ferdous Zannat, James C. Morris, William W. Brennessel, and Patrick L. Holland
Coordination of N-Methylpyrrolidone to Iron(II)
J. Organomet. Chem.   2009694, 4204-4208.  
Meghan M. Clark, William W. Brennessel, Patrick L. Holland
Acta Cryst. C   200965, m391.  More on Decamethylcobaltocene
Ying Yu, Azwana R. Sadique, Jeremy M. Smith, Thomas R. Dugan, Ryan E. Cowley, William W. Brennessel, Christine J. Flaschenriem, Eckhard Bill, Thomas R. Cundari, Patrick L. Holland
The Reactivity Patterns of Low-Coordinate Iron Hydride Complexes
J. Am. Chem. Soc.   2008130, 6624-6638.  
Azwana R. Sadique, William W. Brennessel, and Patrick L. Holland
Reduction of COto CO Using Low-Coordinate Iron: Formation of a Four-Coordinate Iron Dicarbonyl Complex and a Bridging Carbonate Complex
Inorg. Chem.   200847, 784-786.  
Ying Yu, William W. Brennessel, and Patrick L. Holland
Borane B-C Bond Cleavage by a Low-Coordinate Iron Hydride Complex and N-N Bond Cleavage by the Hydridoborate Product
Organometallics  200726, 3217-3226.  
Javier Vela, Jeremy M. Smith, Ying Yu, Nicole A. Ketterer, Christine J. Flaschenriem, Rene J. Lachicotte, Patrick L. Holland
Synthesis and Reactivity of Low-Coordinate Iron(II) Fluoride Complexes and Their Use in the Catalytic Hydrodefluorination of Fluorocarbons
J. Am. Chem. Soc.   2005127, 7857-7870.  
Javier Vela, Jeremy M. Smith, Rene J. Lachicotte, Patrick L. Holland
Alkyl group isomerisation in three-coordinate iron(II) complexes
Chem. Commun.   2002, 2886-2887.  
Jeremy M. Smith, Rene J. Lachicotte, Patrick L. Holland
Three-coordinate, 12-electron organometallic complexes of iron(II): synthesis and insertion of CO to give square pyramidal complexes
Organometallics   200221, 4808-4814.