Energy harvested directly from sunlight offers a desirable approach
toward fulfilling the global need for clean energy. In photosynthesis,
the energy of photons is used to drive the reduction of carbon dioxide
to a variety of higher energy products. This reaction is biologically
important because it allows for storing of the solar energy in the form
of chemical energy, which can be released later in the process of
respiration. Collecting and storing solar energy in chemical bonds, as
nature accomplishes through photosynthesis, is a highly appealing
strategy to solving the energy challenge. The two reactions considered
most often in the context of artificial photosynthesis are the reduction
of carbon dioxide and water. Carbon dioxide has received attention as an
abundant, economical, and renewable C1 feedstock. The catalytic
conversion of carbon dioxide to liquid fuels would positively impact the
global CO2 balance.
Our research will focus on the design, synthesis, and study of
inorganic materials for applications to solar energy conversion. Nature
uses metalloproteins to perform difficult reactions, such as the
reduction of carbon dioxide or water, near the thermodynamic potential
and with high turnover frequencies. With inspiration from the biological
systems, we will develop synthetic homogeneous catalysts that involve
hydrogen bonding networks or hetero-bimetallic species capable of small
molecule activation, and multiple proton and electron transfers. These
synthetic systems will be employed for the reduction of carbon dioxide.
Our program will also focus on the development of catalytic surfaces
that will support homogeneous and heterogeneous catalysts for the
activation of small molecules, such as water or carbon dioxide.
Researchers in the Marinescu group will become experts in the
synthesis and characterization of organic and inorganic species.
Glove-boxes and Schlenk-lines will be routinely utilized for the
synthesis and handling of air- and moisture-sensitive compounds. The
characterization tools for the prepared complexes include NMR, IR, EPR,
UV-VIS spectroscopy and X-ray crystallography. The redox properties
and catalytic activity of these species will be investigated by
electrochemistry. The new electrode materials generated will be
characterized by a variety of surface characterization techniques
including SEM, TEM, XPS, and AFM.
The novel metal complexes and materials synthesized in the Marinescu
group are expected to provide solutions to challenges related to solar
- Marinescu, S. C.; Winkler, J. R.; Gray, H. B. "Molecular Mechanisms of Cobalt Catalyzed Hydrogen Evolution" Proc. Natl. Acad. Sci. USA 2012, 109, 15127-15131.
- This article was featured in Science (Yeston, J. S. "Protons coming and going" Science 2012, 338, 17), C&E News (Jacoby, M. "Pinning down a Cobalt-Catalyzed Hydrogen Evolution" C&E News 2012, 90, 37, 8) and a Caltech press release entitled "Showing the Way to Improved Water-Splitting Catalysts".
- Marinescu, S. C.; Bracher, P. J.; Winkler, J. R.; Gray, H. B. "Solar Fuels" AIP Conf. Proceedings 2013, in press.
- Keith, J. A.; Behenna, D. C.; Sherden, N.; Mohr, J. T.; Ma, S.; Marinescu, S. C.; Nielsen, R. J.; Oxgaard, J.; Stoltz, B. M.; Goddard, W. A., III "The Reaction Mechanism of the Enantioselective Tsuji Allylation: Inner-Sphere and Outer-Sphere Pathways, Internal Rearrangements, and Asymmetric C-C Bond Formation" J. Am. Chem. Soc. 2012, 134, 19050-19060.
- Marinescu, S. C.; Ng, V. W. L.; Lichtscheidl, A. G.; Schrock, R. R.; Müller, P.; Takase, M. K. "Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum" Organometallics 2012, 31, 6336-6343.
- Behenna, D. C.; Mohr, J. T.; Sherden, N. H.; Marinescu, S. C.; Harned, A. M.; Tani, K.; Seto, M.; Ma, S.; Novák, Z.; Krout, M. R.; McFadden, R. M.; Roizen, J. L.; Enquist, J. A., Jr.; White, D. E.; Levine, S. R.; Petrova, K. V.; Iwashita, A.; Virgil, S. C.; Stoltz, B. M. "Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies" Chem. Eur. J. 2011, 17, 14199-14223.
- Marinescu, S. C.; Levine, D. S.; Zhao, Y.; Schrock, R. R.; Hoveyda, A. H. "Isolation of Pure Disubstituted E Olefins through Mo-Catalyzed Z-Selective Ethenolysis of Stereoisomeric Mixtures" J. Am. Chem. Soc. 2011, 133, 11512-11514.
- Marinescu, S. C.; Schrock, R. R.; Müller, P.; Takase, M. K.; Hoveyda, A. H. "Room Temperature Z-Selective Homcoupling of α-Olefins by Tungsten Catalysts" Organometallics 2011, 30, 1780-1782.
- Marinescu, S. C.; King, A. J.; Schrock, R. R.; Singh, R.; Müller, P.; Takase, M. K. "Simple Molybdenum(IV) Olefin Complexes of the Type Mo(NR)(X)(Y)(olefin)" Organometallics 2010, 29, 6816-6828.
- Schrock, R. R.; Jiang, A. J.; Marinescu, S. C.; Simpson, J. H.; Müller, P. "Fundamental Studies of Molybdenum and Tungsten Methylidene and Metallacyclobutane Complexes" Organometallics 2010, 29, 5241-5251.
- Marinescu, S. C.; Schrock, R. R.; Müller, P.; Hoveyda, A. H. "Ethenolysis Reactions Catalyzed by Imido Alkylidene Monopyrrolide (MAP) Complexes of Molybdenum" J. Am. Chem. Soc. 2009, 131, 10840-10841.
- Rendon, N.; Berthoud, R.; Blanc, F.; Gajan, D.; Maishal, T.; Basset, J.-M.; Copéret, C.; Lesage, A.; Emsley, L.; Marinescu, S. C.; Singh, R.; Schrock, R. R. "Well-Defined Silica-Supported Mo-Alkylidene Catalyst Precursors containing one OR Substituent: Methods of Preparation and Structure-Reactivity Relationship in Alkene Metathesis" Chem. Eur. J. 2009, 15, 5083-5089.
- Marinescu, S. C.; Schrock, R. R.; Li, B.; Hoveyda, A. H. "Inversion of Configuration at the Metal in Diastereomeric Imido Alkylidene Monoaryloxide Monopyrrolide Complexes of Molybdenum" J. Am. Chem. Soc. 2009, 131, 58-59.
- Marinescu, S. C.; Singh, R.; Hock, A. S.; Wampler, K. M.; Schrock, R. R.; Müller, P. "Syntheses and Structures of Molybdenum Imido Alkylidene Pyrrolide and Indolide Complexes" Organometallics 2008, 27, 6570-6578.
- Marinescu, S. C.; Toyoki, N.; Mohr, J. T.; Stoltz, B. M. "Homogeneous Pd-Catalyzed Enantioselective Decarboxylative Protonation" Org. Lett. 2008, 10, 1039-1042.
- Keith, J. A.; Behenna, D. C.; Mohr, J. T.; Ma, S.; Marinescu, S. C.; Oxgaard, J.; Stoltz, B. M.; Goddard, W. A., III "The Inner-Sphere Process in the Enantioselective Tsuji Allylation Reaction with (S)-t-Bu-phosphinooxazoline Ligands" J. Am. Chem. Soc. 2007, 129, 11876-11877.
- Marinescu, S. C.; Agapie, T.; Day, M. W.; Bercaw, J. E. "Group 3 Dialkyl Complexes with Tetradentate (L, L, N, O; L = N, O, S) Monoanionic Ligands - Synthesis and Reactivity" Organometallics 2007, 26, 1178-1190.