Robert J. Gilliard, Jr.
Synthetic Chemistry: Main-Group and Organometallic Chemistry, Bond Activation and Catalysis, Hybrid Materials
The Gilliard Research Laboratory focuses its efforts on the synthesis, structure, reactivity and applications of main-group and late transition metal species. We develop novel synthetic methods to access molecules that are relevant to a wide range of energy-related problems. In many cases, the compounds of interest contain reactive or unstable components (e.g., radicals, hydrides, multiple bonds, etc.). Accordingly, we utilize various anaerobic synthetic procedures including Schlenk techniques and inert atmosphere gloveboxes.
Current research themes under investigation include:
Bond Activation and Catalysis Mediated by Main-Group Elements - we are targeting catalysts and catalyst precursors which activate relatively inert chemical bonds (e.g., C-H, N-H, Si-H), critically important processes for tackling our current energy problems. We are also concerned with the interaction of these compounds with important energy-related small molecules such as CO, CO2, and H2.
Hybrid Materials - we are developing novel hybrid inorganic-organic polymers which contain unconventional d- and p-block element components in their structure for advancements in organic light emitting diode (OLED) technologies and molecular electronics.
Heterocycles and Bioactive Organometallics - we are synthesizing novel conjugated heterocycles which contain heavier main-group elements, mimicking the structural features of bioactive transition metal species. The physio-chemistry of these new complexes will be explored for future applications in medicinal chemistry.
An Isolable Magnesium Diphosphaethynolate Complex. Gilliard Jr., Robert J.; Heift, Dominikus; Benkő, Zoltán; Kieser, Jerod M.; Rheingold, Arnold; Grützmacher, Hansjörg; Protasiewicz, John D. Dalton Trans. 2018, DOI: 10.1039/C7DT04539E.
Synthesis of P2C2O2 and P2CO via NHC-Mediated Coupling of the Phosphaethynolate Anion. Gilliard Jr., Robert J.; Suter, Riccardo; Schrader, Erik; Benkő, Zoltán, Rheingold, Arnold; Grützmacher, Hansjörg; Protasiewicz, John D. Chem. Commun. 2017, DOI:10.1039/C7CC07654A.
Insertion of Sodium Phosphaethynolate, Na[OCP], into a Zirconium-Benzyne Complex. Kieser, Jerod M.; Gilliard Jr., Robert J.; Rheingold, Arnold; Grützmacher, Hansjörg, Protasiewicz, John D.; Chem. Commun. 2017, 53, 5110-5112.
From the Parent Phosphinidene-Carbene Adduct NHC=PH to Cationic P4-Rings and P2-Cycloaddition Products. Beil, Andreas; Gilliard Jr., Robert J.; Grützmacher, Hansjörg Dalton Trans. 2016, 45, 2044-2052.
Oxidation of Carbene-Stabilized Diarsenic: Diarsene Dications and Diarsenic Radical Cations. Abraham, Mariham Y.; Wang, Yuzhong; Yaoming, Xie; Gilliard Jr., Robert J.; Wei, Pingrong; Vaccaro, Brian J.; Johnson, Michael K.; Schaefer III, Henry F.; Schleyer, Paul v. R.; Robinson, Gregory H. J. Am. Chem. Soc. 2013, 135, 2486-2488.
Carbene-Stabilized Beryllium Borohydride. Gilliard Jr., Robert J.; Abraham, Mariham Y.; Wang, Yuzhong; Wei, Pingrong; Yaoming, Xie; Quillian, Brandon; Schaefer III, Henry F.; Schleyer, Paul v. R.; Robinson, Gregory H. J. Am. Chem. Soc. 2012, 134, 9953-9955. This manuscript was featured as a JACS Spotlight Article: J. Am. Chem. Soc. 2012, 134, 11299-11300.