Timothy Hanusa

We have extensively used rational ligand design to control the synthesis and reactivity of main-group and transition metal organometallic and coordination complexes. We have also investigated steric effects on the reactivity and magnetic/electrochemical properties of metal complexes, and synthesized precursors to materials with desired electronic/optical properties. Most recently, we are conducting research into the mechanochemical synthesis of organometallic complexes of the s-, p-, and d-block elements, including those with bulky allyl ligands. The grinding or ball milling of reagents provides access to compounds that are not available through conventional solution-based methods, including those with potential catalytic applications. Two particular areas of mechanochemical interest are: 1) the synthesis of low-coordinate metal complexes, as they can display higher reactivity than comparable solvated species, and 2) the control of stereochemistry in solid-state synthesis.

1. Koby, R. F.; Doerr, A. M.; Rightmire, N. R.; Schley, N. D.; Long, B. K.; Hanusa, T. P., An η³-Bound Allyl Ligand on Magnesium in a Mechanochemically Generated Mg/K Allyl Complex. Angew. Chem. Int. Ed. 2020, 59 9542-9548. https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201916410
2. Speight, I. R.; Huskić, I.; Arhangelskis, M.; Titi, H. M.; Stein, R. S.; Hanusa, T. P.; Friščić, T., Disappearing Polymorphs in Metal–Organic Framework Chemistry: Unexpected Stabilization of a Layered Polymorph over an Interpenetrated Three-Dimensional Structure in Mercury Imidazolate. Chem – Eur. J. 2020, 26 (8), 1811-1816. https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201905863
3. Koby, R. F.; Hanusa, T. P.; Schley, N. D., Mechanochemically Driven Transformations in Organotin Chemistry: Stereochemical Rearrangement, Redox Behavior, and Dispersion-Stabilized Complexes. J. Am. Chem. Soc. 2018, 140 (46), 15934-15942. https://doi.org/10.1021/jacs.8b09862
4. Rightmire, N. R.; Hanusa, T. P., Advances in Organometallic Synthesis with Mechanochemical Methods. Dalton Trans. 2016, 45, 2352-2362. http://dx.doi.org/10.1039/C5DT03866A
5. Rightmire, N. R.; Hanusa, T. P.; Rheingold, A. L., Mechanochemical Synthesis of [1,3-(SiMe₃)₂C₃H₃]₃(Al,Sc), a Base-Free Tris(allyl)aluminum Complex and Its Scandium Analogue. Organometallics 2014, 33, 5952–5955. http://dx.doi.org/10.1021/om5009204

1. Koby, R. F.; Hanusa, T. P., Dispersion and distortion in heavy group 2 and lanthanide decamethylmetallocenes: The (C₅Me₅)₂(Sr,Sm) connection. J. Organomet. Chem. 2018, 857, 145-151. https://doi.org/10.1016/j.jorganchem.2017.11.007
2. Boyde, N. C.; Chmely, S. C.; Hanusa, T. P.; Rheingold, A. L.; Brennessel, W. W., Structural Distortions in M[E(SiMe₃)₂]₃ Complexes (M = Group 15, f-Element; E = N, CH): Is Three a Crowd? Inorg. Chem. 2014, 53 (18), 9703-9714. http://dx.doi.org/10.1021/ic501232z
3. Chmely, S. C.; Hanusa, T. P.; Brennessel, W. W., Bis(1,3-trimethylsilylallyl)beryllium. Angew. Chem. Int. Ed. 2010, 49 (34), 5870–5874. http://dx.doi.org/10.1002/anie.201001866
4. Chmely, S. C.; Carlson, C. N.; Hanusa, T. P.; Rheingold, A. L., Classical versus Bridged Allyl Ligands in Magnesium Complexes: The Role of Solvent. J. Am. Chem. Soc. 2009, 131 (18), 6344-6345. http://dx.doi.org/10.1021/ja900998t
5. Quisenberry, K. T.; Smith, J. D.; Voehler, M.; Stec, D. F.; Hanusa, T. P.; Brennessel, W. W., Trimethylsilylated Allyl Complexes of Nickel. The Stabilized Bis(π-allyl)nickel Complex [η³-1,3-(SiMe₃)₂C₃H₃]₂Ni and its Mono(π-allyl)NiX (X = Br, I) Derivatives. J. Am. Chem. Soc. 2005, 127, 4376-4387. http://dx.doi.org/10.1021/ja044308s

Orcid ID: orcid.org/0000-0002-7935-5968
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• Organometallic synthesis
• Coordination compound synthesis
• Generation of active catalytic initiators