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T. Don Tilley

T. Don Tilley

· PMP Tech Chancellor’s Chair in Chemistry; Professor of ChemistryVerified

University of California, Berkeley · Department of Chemical and Biomolecular Engineering

Active 1980–2025

h-index104
Citations38.5k
Papers80495 last 5y
Funding$4.5M
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About

T. Don Tilley, born in 1954, is a distinguished professor of chemistry holding the title of PMP Tech Chancellor’s Chair in Chemistry at the University of California, Berkeley. He completed his B.S. at the University of Texas in 1977 and earned his Ph.D. from the University of California, Berkeley in 1982. His postdoctoral work included NSF Exchange positions at the California Institute of Technology and ETH Zürich, Switzerland. Tilley has held faculty positions at the University of California, San Diego, and has been a faculty member at UC Berkeley since 1994, also serving as a Faculty Senior Scientist at Lawrence Berkeley National Laboratory. His research focuses on organometallic, polymer, and materials chemistry, with particular emphasis on catalysis, synthetic, structural, and reactivity studies on transition metal compounds. His work involves exploring new chemical transformations, developing advanced solid-state materials, and designing catalysts for sustainable energy applications. Tilley has received numerous awards and honors, including election to the National Academy of Science in 2023, fellowships in the American Association for the Advancement of Science and the American Academy of Arts and Sciences, and prestigious awards from the American Chemical Society. His research aims to discover novel inorganic and organometallic systems, elucidate reaction mechanisms, and develop new materials and catalysts for applications in electronics, energy, and catalysis.

Research topics

  • Organic chemistry
  • Chemistry
  • Stereochemistry
  • Combinatorial chemistry
  • Nanotechnology
  • Materials science

Selected publications

  • Vanadium–Cobalt O≡VCo3O4 Oxo Cubanes from V/Co Redox Exchange

    ChemRxiv · 2025-12-09

    preprintSenior author

    The synthesis of a novel vanadium-cobalt oxo cubane [O≡VCo3(μ3-OH)(μ3-O)3(OAc)4(t-Bupy)3]+ (OAc = acetate, t-Bupy = 4-tertbutylpyridine) occurs by way of a metal-metal exchange reaction between the Co4(μ3-O)4(OAc)4(t-Bupy)4 cubane and VCl4(THF)2. Mechanistic investigations reveal that the terminal oxo ligand originates from water, and that a proton source is critical for the metal-metal exchange. The solid-state structure of the [O≡VCo3O4]+ cubane is more distorted from an idealized cubane geometry than previously reported [MCo3O4] heterometallic cubanes (M = Ru, Mn). The cluster is readily deprotonated by basic alumina to produce the neutral cluster, O≡VCo3(μ3-O)4(OAc)4(t-Bupy), the solid-state structure of which reveals retention of the oxo-cubane motif. The observed bonding and reactivity are rationalized with density functional theory, which indicates that the vanadium center does not significantly contribute to the occupied fron-tier molecular orbitals. Electrochemical studies support a quasireversible one-electron oxidation event at 0.85 V vs. Fc/Fc+ in acetonitrile but attempts to isolate the oxidized species instead gave the protonated cluster resulting from C–H bond activation of the solvent.

  • Dynamically Chiral Expanded Helicenes

    Journal of the American Chemical Society · 2025-11-22 · 2 citations

    articleSenior authorCorresponding

    Expanded helicenes are a class of chiral nanographenes with a screw-shaped skeleton and a larger diameter than their classical ortho-fused counterparts. The flexibility of this internal cavity results in helicenes that are often difficult to isolate as single enantiomers. Expanded helicenes are therefore an intriguing target for exploration of dynamic chirality, a phenomenon resulting from introduction of chiral auxiliaries to control structure in a racemic system. This contribution describes installation of chiral amine substituents into the cavity of a diformyl expanded [11]-helicene by mild, efficient, and reversible imine condensations. The resulting helicenes display strong molar circular dichroism up to |Δε| = 300 M–1 cm–1 and absorption dissymmetry factors of |gabs| = 0.010. The magnitude of circular dichroism can be varied by using different chiral amine substituents, which is correlated to the diastereomeric ratios of the helicenes. This is the first instance of dynamic chirality being used to observe a chiroptic response in expanded helicenes and is a significant synthetic improvement over methods which require conventional enantiomer resolution.

  • Unsaturated Osmium–Tin Complexes from Reactions of Osmium Polyhydrides

    Organometallics · 2025-12-18

    articleSenior authorCorresponding

    Reactions of the osmium polyhydride complexes Cp*OsH5 (Cp* = η5-C5Me5) and Cp*2Os2(μ-H)4 with the amidostannylene DMPSnN(SiMe3)2 (DMP = C6H3-2,6-Mes2, Mes = mesityl) are reported. Treatment of Cp*OsH5 with DMPSnN(SiMe3)2 in n-pentane results in the rapid formation of osmiostannylene Cp*OsH4SnDMP (1), which precipitates from solution. While 1 is stable in the solid state, it decomposes in solution to form the μ2-stannylyne complex Cp*H4Os(μ-SnDMP)OsH3Cp* (2). Complex 2 can be prepared in a targeted manner by the reaction of Cp*OsH5 with DMPSnN(SiMe3)2 in toluene over an extended period. Cp*2Os2(μ-H)4 reacts with DMPSnN(SiMe3)2 to form the unique μ2-hydridostannylene complex Cp*2Os2(μ-H)2{μ-Sn(H)DMP} (3).

  • Dynamically Chiral Expanded Helicenes

    ChemRxiv · 2025-09-09

    preprintOpen accessSenior author

    Expanded helicenes are a class of chiral nanographenes with a screw-shaped skeleton and a larger diameter than their classical ortho-fused counterparts. The flexibility of this internal cavity results in helicenes that are often difficult to isolate as single enantiomers. Expanded helicenes are therefore an intriguing target for exploration of dynamic chirality, a phenomenon resulting from introduction of chiral auxiliaries to control structure in a racemic system. This contribution describes installation of chiral amine substituents into the cavity of a diformyl expanded [11]- helicene by mild, efficient, and reversible imine condensations. The resulting helicenes display strong molar circular dichroism up to │Δε│= 300 M-1cm-1 and absorption dissymmetry factors of │gabs│ = 0.010. The magnitude of circular dichroism can be varied by using different chiral amine substituents, which is correlated to the diastereomeric ratios of the helicenes. This is the first instance of dynamic chirality being used to observe a chiroptic response in expanded helicenes and is a significant synthetic improvement over methods which require conventional enantiomer resolution.

  • Dicopper(<scp>i</scp>) complexes of a binucleating, dianionic, naphthyridine bis(amide) ligand

    Dalton Transactions · 2025-01-01 · 3 citations

    articleOpen accessSenior authorCorresponding

    . DFT calculations suggest a more ionic bonding character and weaker Cu-Cu interactions in the NBDA complexes compared to those with other 1,8-naphthyridine-based ligands. This is congruent with intermetallic separations of over 3 Å induced by relatively strong coordination of the copper atoms to the amide nitrogen donor atoms observed in the solid state molecular structures.

  • Synthesis of Metallostannylenes from Transition Metal Polyhydride Complexes

    Journal of the American Chemical Society · 2025-10-08 · 1 citations

    articleSenior authorCorresponding

    Syntheses of high-valent open-chain metallostannylene hydride complexes from transition metal polyhydride complexes and aryl-substituted amidostannylenes are reported. The reaction of (MeBDIDipp)IrH4 (MeBDIDipp = (Dipp)NC(Me)CH(Me)CN(Dipp); Dipp = 2,6-diisopropylphenyl) with DMPSnN(SiMe3)2 (DMP = C6H3-2,6-Mes2, Mes = mesityl) gives access to metallostannylene (MeBDIDipp)IrH3SnDMP (1) with HN(SiMe3)2 as the byproduct. Similarly, treatment of Cp*IrH4 (Cp* = η5-C5Me5) with DMPSnN(SiMe3)2 leads to the formation of Cp*IrH3SnDMP (2). In contrast to 1, 2 cleanly reacts with a second equivalent of DMPSnN(SiMe3)2, allowing for the synthesis of bis(metallostannylene) Cp*IrH2(SnDMP)2 (3). Additionally, the synthesis and characterization of two new amidostannylenes DMPSn[N(Dipp)(SiMe3)] (4) and TripSn[N(Dipp)(SiMe3)] (5; Trip = 2,4,6-triisopropylphenyl) is presented. While the reaction of Cp*IrH4 with 4 represents an alternative route to 2, treatment of (MeBDIDipp)IrH4 with 5 yields the amidostannylene complex (MeBDIDipp)(H)2Ir═Sn(Trip){N(Dipp)(SiMe3)} (6) with concomitant release of H2, rendering stannylene coordination a reaction pathway that competes with Sn–N bond cleavage and metallostannylene formation. Within the broader context of transition metal–main group element compounds, metallostannylene formation is characterized as a formal deprotonation of the transition metal polyhydride complex by the amidostannylene. Notably, the ambiphilicity of amidostannylenes, which distinguishes them from tetravalent amidostannanes, appears to be essential for efficient Ir–Sn bond formation.

  • Discovery of an Interlocked and Interwoven Molecular Topology in Nanocarbons via Dynamic C–C Bond Formation

    Journal of the American Chemical Society · 2025-05-23 · 10 citations

    articleOpen accessSenior authorCorresponding

    Topologically complex carbon nanostructures are an exciting but largely unexplored class of materials due to their challenging synthesis. Previous methods are low yielding because they rely on irreversible Csp2–Csp2 bond formation, which necessitates complex templating strategies to enforce entanglement. Here, reversible zirconocene coupling of alkynes is developed as a new method to access complex molecular topologies, where dynamic C–C bond formation facilitates entanglement under thermodynamic control, allowing the use of simple precursors without the need for preassembly. This strategy enables the scalable, high-yield synthesis of three topologically distinct nanocarbons, including the serendipitous discovery of a structure containing a new topological motif that was not previously identified or realized synthetically. This motif, consisting of an unusual combination of interlocking and interweaving, was recognized to be generalizable to a new topological class of molecules, introduced here as perplexanes.

  • Correction: Dicopper(<scp>i</scp>) complexes of a binucleating, dianionic, naphthyridine bis(amide) ligand

    Dalton Transactions · 2025-01-01

    erratumOpen accessSenior authorCorresponding

    Correction for ‘Dicopper( i ) complexes of a binucleating, dianionic, naphthyridine bis(amide) ligand’ by Laurent Sévery et al. , Dalton Trans. , 2025, https://doi.org/10.1039/d5dt00034c.

  • CCDC 2391276: Experimental Crystal Structure Determination

    OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) · 2024-12-07

    articleOpen accessSenior author

    An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  • Diborane Reductions of CO<sub>2</sub> and CS<sub>2</sub> Mediated by Dicopper μ-Boryl Complexes of a Robust Bis(phosphino)-1,8-naphthyridine Ligand

    Organometallics · 2024-05-03 · 5 citations

    articleOpen accessSenior authorCorresponding

    A dinucleating 1,8-naphthyridine ligand featuring fluorene-9,9-diyl-linked phosphino side arms (PNNPFlu) was synthesized and used to obtain the cationic dicopper complexes 2, [(PNNPFlu)Cu2(μ-Ph)][NTf2]; [NTf2] = bis(trifluoromethane)sulfonimide, 6, [(PNNPFlu)Cu2(μ-CCPh)][NTf2], and 3, [(PNNPFlu)Cu2(μ-OtBu)][NTf2]. Complex 3 reacted with diboranes to afford dicopper μ-boryl species (4, with μ-Bcat; cat = catecholate and 5, with μ-Bpin; pin = pinacolate) that are more reactive in C(sp)–H bond activations and toward activations of CO2 and CS2, compared to dicopper μ-boryl complexes supported by a 1,8-naphthyridine-based ligand with di(pyridyl) side arms. The solid-state structures and DFT analysis indicate that the higher reactivities of 4 and 5 relate to changes in the coordination sphere of copper, rather than to perturbations on the Cu–B bonding interactions. Addition of xylyl isocyanide (CNXyl) to 4 gave 7, [(PNNPFlu)Cu2(μ-Bcat)(CNXyl)][NTf2], demonstrating that the lower coordination number at copper is chemically significant. Reactions of 4 and 5 with CO2 yielded the corresponding dicopper borate complexes (8, [(PNNPFlu)Cu2(μ-OBcat)][NTf2]; 9, [(PNNPFlu)Cu2(μ-OBpin)][NTf2]), with 4 demonstrating catalytic reduction in the presence of excess diborane. Related reactions of 4 and 5 with CS2 provided insertion products 10, {[(PNNPFlu)Cu2]2[μ-S2C(Bcat)2]}[NTf2]2, and 11, [(PNNPFlu)Cu2(μ,κ2-S2CBpin)][NTf2], respectively. These products feature Cu–S–C–B linkages analogous to those of proposed CO2 insertion intermediate.

Recent grants

Frequent coauthors

  • Micah S. Ziegler

    Lawrence Berkeley National Laboratory

    208 shared
  • Odile Eisenstein

    Université de Montpellier

    159 shared
  • Noémi Barros

    Université de Perpignan

    125 shared
  • Alexis T. Bell

    109 shared
  • Amélie Nicolay

    University of California, Berkeley

    107 shared
  • J.L. McBee

    106 shared
  • Laurent Maron

    Commissariat à l'Énergie Atomique et aux Énergies Alternatives

    100 shared
  • Daniel S. Levine

    University of California, Berkeley

    94 shared

Labs

Education

  • PhD, Chemistry

    University of California Berkeley

    1981
  • BS, Chemistry

    The University of Texas at Austin

    1977

Awards & honors

  • Alfred P. Sloan Fellow (1988-90)
  • Union Carbide Innovation Recognition Awards (1991, 1992)
  • Japan Society for the Promotion of Science Fellow (1993)
  • Alexander von Humboldt Senior Scientist (1998)
  • Fellow of the American Association for the Advancement of Sc…
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