Meet Organometallics’ 2021 Distinguished Author Award Recipient - ACS Axial

Meet Organometallics’ 2021 Distinguished Author Award Recipient

Co-sponsored by the ACS Division of Organic Chemistry, the ACS Division of Inorganic Chemistry, and Organometallics, this annual award recognizes authors of exceptional articles published in Organometallics in the previous two calendar years that emphasize the importance of organometallic chemistry and have made a profound impact on the field.

Meet the Recipient 

Professor Robert J. Gilliard, Jr. is recognized for his dynamic and ground-breaking research in main-group chemistry, in particular his group’s work on novel complexes and electronic structures of magnesium and beryllium. He is succeeded by 2020 recipient, Viktoria H. Gessner, who was recognized for her research on carbanionic species as ligands in main-group and transition-metal chemistry.

Learn more about Professor Gilliard in this interview.

What does it mean to you to be the recipient of this award?

I am grateful for this recognition. There is arguably no greater professional honor than to be nominated and selected by those in your own broad field of study, organometallic chemistry; they know the impact, challenges, and experimental difficulty of the science better than anyone. This Organometallics Distinguished Author Award reflects the hard work my students, postdocs, and collaborators have put forth over the last several years to understand chemical bonding and reactions involving the alkaline earth metals, and it is truly a pleasure to be named considering the international list of past award recipients, all of which I have great respect for.

What prompted you to study this field of chemistry?

My years as an undergraduate researcher in the Smith group at Clemson University were truly formative, and I developed an appreciation for both inorganic and organic chemistry. At the time we were synthesizing a range of organometallic transition metal compounds based on classic meta-terphenyl and carbene ligands, which I still use to this day. As I continued to progress through the educational system I kept a file of ideas and areas I wanted to pursue based on the chemical literature I read. Some of those ideas were explored and published before I became a faculty member but there are still so many unanswered questions, and there’s certainly no shortage of scientific problems. Right after I joined the faculty at the University of Virginia I recall listening to Hary Gray’s advice to early-career faculty members at an ACS meeting, I believe it was at the 2017 C&EN Talented 12 symposium. I am paraphrasing but he said if you think you have something else to add to the discussion, do it. As a student, I remember reading fascinating s-block papers by Cameron Jones, Phil Power, Sjoerd Harder, Mike Hill, Robert Mulvey and many others. It was clear that earth-abundant alkaline earth metals have tremendous potential in redox chemistry and catalysis. However, that requires systematic studies in ligand design and structure and bonding, and I am fortunate to now be able to help push the field forward.

What are some of the important applications that you are working on that will benefit society?

We, and others, are discovering that the alkaline earth metals possess a degree of redox flexibility. The preparation of unprecedented low-valent alkaline earth complexes and highly Lewis acidic compounds is already resulting in the rapid advancement of s-block metal-mediated catalysis and small molecule activation. Because the alkaline earth elements are some of the most abundant metals we have access to these discoveries may result in new catalysts that serve as low-cost alternatives in modern industrial processes that currently rely on expensive precious metals. My group also continues to study hydrogen-rich group 2 complexes as molecular vehicles in hydrogen storage chemistry and we plan to report on this topic later this year. These molecules could play a role in alternative fuel technologies and minimally they will serve as excellent molecular models for dehydrogenation processes that are usually difficult to probe.

While we are being recognized for magnesium and beryllium chemistry, my group is also working on various aspects of organoboron chemistry, with a focus on accessing new redox states in boron-doped polycyclic aromatic hydrocarbon materials. I believe these compounds have the potential to be used for further synthetic elaboration in the preparation of unusual materials-relevant heterocycles that cannot be obtained with traditional starting materials. We seek to investigate structure-function relationships with the expectation that our chemistry will have an impact on next-generation electronics and display technologies.

Tell us about your research philosophy.

Research is challenging, and the hours are long, so I always believed that if I am going to do this it is going to be fun. While there have been many days where I have been exhausted, I enjoy going to work every day, the research is exciting, and my job is a lot of fun. A large part of the reason I can say that is because of the fantastic students in my research group. In the continuous pursuit of research excellence, I never want to lose sight of the major reason I was afforded this academic position in the first place, which is to provide top-notch education, training, and mentoring to the next generation of science leaders, and I try to do that first with the people on my own team.

What’s next in your research?

We have synthesized a range of s- and p-block organometallic compounds and over the next several years we will take a detailed look at chemical reactivity, including small-molecule activation. Of course, we will continue to pursue fundamental organometallic chemistry, but there is a subset of our research portfolio that will focus on examining the optical properties of main-group functional materials. We have already taken the first steps in this process and the device properties of some of our compounds are being explored by chemical engineering collaborators.

Is there anything else that you would like to share?

I would like to thank all of the mentors, main-group colleagues, and collaborators that have supported me and my research group. I am also grateful to the undergraduates, graduate students, and postdocs in my group for their hard work and dedication to the science.

Read a Selection of Papers from Professor Gilliard:

N-Heterocyclic Carbene-Mediated Ring Opening of Reduced Diazamagnesacycles
Organometallics 2020, 39, 24, 4575–4583
DOI: 10.1021/acs.organomet.0c00620
Two Carbenes versus One in Magnesium Chemistry: Synthesis of Terminal Dihalide, Dialkyl, and Grignard Reagents
Organometallics 2019, 38, 3, 688–696
DOI: 10.1021/acs.organomet.8b00866
Tris(carbene) Stabilization of Monomeric Magnesium Cations: A Neutral, Nontethered Ligand Approach
Organometallics 2020, 39, 23, 4329–4339
DOI: 10.1021/acs.organomet.0c00462

A Stable, Crystalline Beryllium Radical Cation
J. Am. Chem. Soc. 2020, 142, 10, 4560–4564
DOI: 10.1021/jacs.9b13777

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