Science

Research

We pursue fundamental questions in inorganic and organometallic chemistry, with expertise in the synthesis and study of reactive, air-sensitive metal complexes.

Our Approach

The Fortier group specializes in the synthesis, purification, crystallization, handling, and characterization of air- and water-sensitive molecules and paramagnetic complexes. We use a combination of synthetic inorganic chemistry, X-ray crystallography, spectroscopy, and computational methods to understand the electronic structures and reactivity of novel metal complexes.

Fuming flask with uranium complex
22Ti

Low-Valent Metal Chemistry

A central theme of our research is the synthesis and study of metals in unusually reduced oxidation states, which give rise to highly reactive species. A particular focus is the reduction of highly electropositive elements such as the early-metals and f-elements, where the thermodynamic driving force can generate potent reductants capable of multi-electron transfer. In this context, we have synthesized "molecular capacitors" capable of 8-electron discharge. These supercharged metal complexes show promise for base metal redox catalysis involving two-electron redox cycling, a feature typically associated with precious metals.

Our group has developed novel synthetic strategies for accessing and stabilizing low-valent complexes of titanium, uranium, and other metals, and we use a combination of X-ray crystallography, spectroscopy, and computation to characterize their structure and reactivity.

Ti-thiophene TOC graphic

Representative topics:

Low-valent titanium synthons Redox chemistry of highly reduced complexes C–H and small molecule activation Uranium arene and sandwich complexes
92U

Uranium and F-Element Science

The f-block elements exhibit chemistry that is distinct from transition metals, owing to the unique spatial and energetic properties of f-orbitals. We investigate the structure, bonding, and reactivity of uranium and other f-element complexes to better understand the fundamental principles that govern actinide and lanthanide chemistry. In the actinides, their unique 5f and 6d/7s/7p valence orbital combinations hold potential for reactivity patterns that are, in principle, inaccessible to transition metals, making this an important frontier for both fundamental chemical understanding and reactivity discovery.

Our group has made contributions to uranium carbene, nitride, and arene chemistry, including the first examples of unsupported uranium arenide sandwich complexes.

Uranium anthracenide dimer TOC graphic

Representative topics:

Uranium–carbon bonding Comparative f-block chemistry (Ce, U, Np, Pu) XAS and advanced spectroscopy Highly reduced arene complexes
26Fe

Late 3d-Metal Chemistry

Not all of our work is centered on low-valent, electropositive metals. We also investigate late first-row transition-metal complexes, particularly iron and cobalt systems, that feature reactive metal–ligand multiple bonds. These studies use bulky guanidinate ligands to stabilize unusual bonding motifs and examine how ligand environment controls structure, electronic configuration, and reactivity.

A central goal of this work is to prepare isolable iron and cobalt complexes with highly reactive multiple-bond character, including mono- and bimetallic nitride species. These compounds provide a platform for studying bond activation and redox chemistry at earth-abundant metals.

Dicobalt nitride TOC graphic

Representative topics:

Iron and cobalt guanidinate complexes Metal–ligand multiple bonds Iron and dicobalt nitrides Earth-abundant redox catalysis
L

Ligand Design

Enabling access to highly reactive and unusual metal complexes requires careful design of the ligand environment. We design and synthesize sterically demanding and electronically tunable ancillary ligands that can stabilize reactive metal centers and enforce unusual coordination geometries and oxidation states.

Our ligand design efforts are tightly integrated with our synthetic goals, allowing us to access metal complexes that may otherwise be too reactive to isolate and study.

Ligand design TOC graphic

Representative topics:

Super bulky guanidinate and amide ligands Redox-active ligand platforms Ligands for low-coordinate complexes

Experimental Techniques

New compounds are characterized using complementary structural, spectroscopic, magnetic, and electronic methods that reveal their composition, bonding, and electronic structure.

NMR

Nuclear Magnetic Resonance

scXRD

Single-Crystal X-Ray Diffraction

XANES

X-Ray Absorption Near-Edge Spectroscopy

EPR

Electron Paramagnetic Resonance

SQUID

SQUID Magnetometry

XPS

X-Ray Photoelectron Spectroscopy

Synthesis is carried out using rigorously inert Schlenk-line and glovebox techniques, with additional characterization by X-ray diffraction analysis, NMR spectroscopy, electrochemistry, and other advanced analytical methods.