William B. Tolman | |
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Born | William Baker Tolman May 20, 1961 |
Nationality | American |
Alma mater | University of California, Berkeley Ph.D. (1987) Wesleyan University B.A. (1983) |
Known for | Bioinorganic chemistry of copper and dioxygen |
Awards | ACS Award for Distinguished Service in the Advancement of Inorganic Chemistry (2017) |
Scientific career | |
Fields | Bioinorganic chemistry |
Institutions | University of St. Thomas (2022 - Current) Washington University in St. Louis (2018-2022) Contents
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Thesis | Photochemistry and ligand substitution chemistry of (fulvalene) diruthenium (tetracarbonyl) (1987) |
Doctoral advisor | Peter C. Vollhardt |
Other academic advisors | Alan R. Cutler, Stephen J. Lippard |
Website | sites |
William B. Tolman (born May 20, 1961, in Cleveland, Ohio) an American inorganic chemist focusing on the synthesis and characterization of model bioinorganic systems, and organometallic approaches towards polymer chemistry. He has served as Editor in Chief of the ACS journal Inorganic Chemistry, [1] and as a Senior Investigator at the NSF Center for Sustainable Polymers. [2] Tolman is a Fellow of the American Association for the Advancement of Science and the American Chemical Society. [3]
Tolman was born on May 20, 1961, in Cleveland, Ohio, but grew up in Chelmsford, Massachusetts. [4] [3] He received his B.A. in chemistry from Wesleyan University in 1983, where he conducted organometallic chemistry research with Alan R. Cutler. [3] [5] With Culter, Tolman studied the bimetallic activation of coordinated ligands of molybdenum cyclopentadienyl complexes. [6]
Tolman then moved on to graduate studies at the University of California, Berkeley, where he worked in the laboratory of Prof. K. Peter C. Vollhardt as a W. R. Grace Graduate Fellow. [4] [7] In Vollhardt's laboratory, Tolman studied photochemistry [8] and ligand substitution reactions of bimetallic coordination complexes with the fulvalene ligand. [9] [10] Tolman graduated with a Ph.D. in chemistry in 1987. [3]
He then conducted his postdoc in the laboratory of Prof. Stephen J. Lippard at the Massachusetts Institute of Technology with the support of a fellowship from the American Cancer Society. With Prof. Lippard, Tolman synthesized novel ligands for coordination complexes that model the active sites of metalloproteins. [11] He then synthesized complexes that model nonheme diiron proteins, and studied their reactivity with O2. [12] [13]
Tolman began his independent career in 1990, as an assistant professor in the Department of Chemistry at the University of Minnesota, Twin Cities (UMN). [3] He was appointed a Distinguished McKnight University Professor in 2000. [14] He previously served as the Chair of the Department of Chemistry at UMN, from 2009 to 2016. [3] [15] In 2018, Tolman moved with his research group to Washington University in St. Louis. [16] Generally, Tolman's research group works on the synthesis of bioinorganic coordination complexes that model the active sites of metalloproteins, as well as the synthesis of organometallic complexes for the polymerization of cyclic esters. [3]
In the summer of 2022, Tolman became the dean of the College of Arts and Sciences at the University of St. Thomas, in St. Paul, Minnesota. [17]
Tolman's work in the bioinorganic field focuses on Cu-O adducts, specifically copper proteins whose diverse, biological functions include: O2 transport, aromatic ring oxidations, biogenesis of hormones. [18] His work studies the potential of 1:1 Cu/O2 adducts as catalytic species, which have been known as transient intermediates for more commonly studied 2:1 and even 3:1 Cu/O2 molecules. These complexes, while kinetically favored in formation are thermodynamically unstable due to negative entropy values, thus making them more difficult to isolate. [18] Although, increasing ligand sizes on these 1:1 adducts did correlate with slower reaction rate constants; advantageous for isolating and studying these complexes. [1]
Furthermore, his work on high and mixed valent copper species including [CuOH]+2 and its conjugate base, [CuO]+ is also very notable. His work with [CuOH]+2 reveals a high reactivity with C-H and O-H bonds as compared to its conjugate acid pair. [1] This is of importance when trying to replicate biological mechanisms, such as copper-catalyzed oxidation in vitro.
His research has greatly contributed to the discovery and characterization of new biomimetic species. It is his goal to not only identify these compounds, but to comprehensively understand the intermediates and mechanisms with which they play crucial roles in facilitating. In the case of Cu/O2 adducts, realizing their biological role and function in copper containing enzymes can give rise to new insights on their biomimetic properties. [1]
Additionally, his lab is searching for alternative, synthetic oxidative catalysis. This includes designing biochemically inspired synthetic catalysts as well as trying O2 as a candidate for controlled, in vitro oxidation. Due to high abundances and relatively strong stabilizing capabilities within biological reactions, iron and copper enzymes inspire biomimetic synthetic catalysts. Although these reactions perform with high accuracy and selectivity within the body, many challenges arise when working with O2 in vitro because of the undesired and potentially harmful side products that can be generated. [19]
Tolman's work on organometallic polymerization catalysis focuses on the development of new metal catalysts for the more efficient polymerization of lactones into biodegradable polymers. An example of this work is the use of Zn(II) or Fe(III) alkoxide catalysts, which can polymerize lactide (LA) into polylactic acid (PLA). [21] [20] PLA is of great interest because it is both biodegradable and a renewable resource. [21] [22] While there are many well known catalysts available to synthesize PLA, not much is known about their mechanism of catalysis - this proves problematic in the design of new and more efficient catalysts. Thus, Tolman's group is pursuing the synthesis and characterization of less structurally complex catalysts. [23] His research has showed that catalysts with lower coordination numbers have higher polymerization activities. [20] His Zn(II) alkoxide catalyst, for example, produced PLA with a high molecular weight at a relatively fast rate.
As UMN Chemistry Department Chair in 2017, Tolman was one of four administrators notified about, and provided the results of, an investigation into allegations involving UMN biochemistry and chemistry professor Gianluigi Veglia's. [24] Tolman left UMN the following year for a position at Washington University in St. Louis. [16]
Tolman is the recipient of many awards for his research, including an ACS Award for Distinguished Service in the Advancement of Inorganic Chemistry in 2017, [25] [26] the Charles E. Bowers Teaching Award from the University of Minnesota in 2012, [27] a Alexander von Humboldt Foundation Research Award for 2004–2005, [3] a Buck-Whitney Medal from the ACS Eastern New York Section in 2001, [3] a Camille & Henry Dreyfus Teacher–Scholar Award in 1999, [28] and a Searle Scholars Award in 1992. [29]
He was elected a Fellow of the American Chemical Society in 2010, [30] and a Fellow of the American Association for the Advancement of Science in 2006. [31]
Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide, cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.
The azide-alkyne Huisgen cycloaddition is a 1,3-dipolar cycloaddition between an azide and a terminal or internal alkyne to give a 1,2,3-triazole. Rolf Huisgen was the first to understand the scope of this organic reaction. American chemist Karl Barry Sharpless has referred to this cycloaddition as "the cream of the crop" of click chemistry and "the premier example of a click reaction".
Salen refers to a tetradentate C2-symmetric ligand synthesized from salicylaldehyde (sal) and ethylenediamine (en). It may also refer to a class of compounds, which are structurally related to the classical salen ligand, primarily bis-Schiff bases. Salen ligands are notable for coordinating a wide range of different metals, which they can often stabilise in various oxidation states. For this reason salen-type compounds are used as metal deactivators. Metal salen complexes also find use as catalysts.
Photosensitizers are light absorbers that alters the course of a photochemical reaction. They usually are catalysts. They can function by many mechanisms, sometimes they donate an electron to the substrate, sometimes they abstract a hydrogen atom from the substrate. At the end of this process, the photosensitizer returns to its ground state, where it remains chemically intact, poised to absorb more light. One branch of chemistry which frequently utilizes photosensitizers is polymer chemistry, using photosensitizers in reactions such as photopolymerization, photocrosslinking, and photodegradation. Photosensitizers are also used to generate prolonged excited electronic states in organic molecules with uses in photocatalysis, photon upconversion and photodynamic therapy. Generally, photosensitizers absorb electromagnetic radiation consisting of infrared radiation, visible light radiation, and ultraviolet radiation and transfer absorbed energy into neighboring molecules. This absorption of light is made possible by photosensitizers' large de-localized π-systems, which lowers the energy of HOMO and LUMO orbitals to promote photoexcitation. While many photosensitizers are organic or organometallic compounds, there are also examples of using semiconductor quantum dots as photosensitizers.
In coordination chemistry, the ligand cone angle is a measure of the steric bulk of a ligand in a transition metal coordination complex. It is defined as the solid angle formed with the metal at the vertex and the outermost edge of the van der Waals spheres of the ligand atoms at the perimeter of the cone. Tertiary phosphine ligands are commonly classified using this parameter, but the method can be applied to any ligand. The term cone angle was first introduced by Chadwick A. Tolman, a research chemist at DuPont. Tolman originally developed the method for phosphine ligands in nickel complexes, determining them from measurements of accurate physical models.
Organonickel chemistry is a branch of organometallic chemistry that deals with organic compounds featuring nickel-carbon bonds. They are used as a catalyst, as a building block in organic chemistry and in chemical vapor deposition. Organonickel compounds are also short-lived intermediates in organic reactions. The first organonickel compound was nickel tetracarbonyl Ni(CO)4, reported in 1890 and quickly applied in the Mond process for nickel purification. Organonickel complexes are prominent in numerous industrial processes including carbonylations, hydrocyanation, and the Shell higher olefin process.
In chemistry, a (redox) non-innocent ligand is a ligand in a metal complex where the oxidation state is not clear. Typically, complexes containing non-innocent ligands are redox active at mild potentials. The concept assumes that redox reactions in metal complexes are either metal or ligand localized, which is a simplification, albeit a useful one.
The Liebeskind–Srogl coupling reaction is an organic reaction forming a new carbon–carbon bond from a thioester and a boronic acid using a metal catalyst. It is a cross-coupling reaction. This reaction was invented by and named after Jiri Srogl from the Academy of Sciences, Czech Republic, and Lanny S. Liebeskind from Emory University, Atlanta, Georgia, USA. There are three generations of this reaction, with the first generation shown below. The original transformation used catalytic Pd(0), TFP = tris(2-furyl)phosphine as an additional ligand and stoichiometric CuTC = copper(I) thiophene-2-carboxylate as a co-metal catalyst. The overall reaction scheme is shown below.
In organic chemistry, a cross-coupling reaction is a reaction where two different fragments are joined. Cross-couplings are a subset of the more general coupling reactions. Often cross-coupling reactions require metal catalysts. One important reaction type is this:
Organocobalt chemistry is the chemistry of organometallic compounds containing a carbon to cobalt chemical bond. Organocobalt compounds are involved in several organic reactions and the important biomolecule vitamin B12 has a cobalt-carbon bond. Many organocobalt compounds exhibit useful catalytic properties, the preeminent example being dicobalt octacarbonyl.
Dioxygen complexes are coordination compounds that contain O2 as a ligand. The study of these compounds is inspired by oxygen-carrying proteins such as myoglobin, hemoglobin, hemerythrin, and hemocyanin. Several transition metals form complexes with O2, and many of these complexes form reversibly. The binding of O2 is the first step in many important phenomena, such as cellular respiration, corrosion, and industrial chemistry. The first synthetic oxygen complex was demonstrated in 1938 with cobalt(II) complex reversibly bound O2.
Metal carbon dioxide complexes are coordination complexes that contain carbon dioxide ligands. Aside from the fundamental interest in the coordination chemistry of simple molecules, studies in this field are motivated by the possibility that transition metals might catalyze useful transformations of CO2. This research is relevant both to organic synthesis and to the production of "solar fuels" that would avoid the use of petroleum-based fuels.
Melanie Sarah Sanford is an American chemist, currently the Moses Gomberg Distinguished University Professor of Chemistry and Arthur F. Thurnau Professor of Chemistry at the University of Michigan. She is a Fellow for the American Association for the Advancement of Science, and was elected a member of the National Academy of Sciences and the American Academy of Arts and Sciences in 2016. She has served as an executive editor of the Journal of the American Chemical Society since 2021, having been an associate editor of the since 2014.
Parisa Mehrkhodavandi is a Canadian chemist and Professor of Chemistry at the University of British Columbia (UBC). Her research focuses on the design of new catalysts that can effect polymerization of sustainably sourced or biodegradable polymers.
Clark Landis is an American chemist, whose research focuses on organic and inorganic chemistry. He is currently a Professor of Chemistry at the University of Wisconsin–Madison. He was awarded the ACS Award in Organometallic Chemistry in 2010, and is a fellow of the American Chemical Society and the American Association for the Advancement of Science.
A lanthanocene is a type of metallocene compound that contains an element from the lanthanide series. The most common lanthanocene complexes contain two cyclopentadienyl anions and an X type ligand, usually hydride or alkyl ligand.
Xile Hu is a Swiss chemist specialized in catalysis. He is a professor in chemistry at EPFL and leads the Laboratory of Inorganic Synthesis and Catalysis at the School of Basic Sciences.
Paula L. Diaconescu is a Romanian-American chemistry professor at the University of California, Los Angeles. She is known for her research on the synthesis of redox active transition metal complexes, the synthesis of lanthanide complexes, metal-induced small molecule activation, and polymerization reactions. She is a fellow of the American Association for the Advancement of Science.
Coinage metal N-heterocyclic carbene (NHC) complexes refer to transition metal complexes incorporating at least one coinage metal center (M = Cu, Ag, Au) ligated by at least one NHC-type persistent carbene. A variety of such complexes have been synthesized through deprotonation of the appropriate imidazolium precursor and metalation by the appropriate metal source, producing MI, MII, or MIII NHC complexes. While the general form can be represented as (R2N)2C:–M (R = various alkyl or aryl groups), the exact nature of the bond between NHC and M has been investigated extensively through computational modeling and experimental probes. These results indicate that the M-NHC bond consists mostly of electrostatic attractive interactions, with some covalent bond character arising from NHC to M σ donation and minor M to NHC π back-donation. Coinage metal NHC complexes show effective activity as catalysts for various organic transformations functionalizing C-H and C-C bonds, and as antimicrobial and anticancer agents in medicinal chemistry.
Copper forms a rich variety of compounds, usually with oxidation states +1 and +2, which are often called cuprous and cupric, respectively. Copper compounds, whether organic complexes or organometallics, promote or catalyse numerous chemical and biological processes.
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