Department of Chemistry

C-C Bond Formation Involving High Valent Nickel

The use of the tridentate ligand Me3tacn and the -CH2CMe2-o-C6H4- (cycloneophyl) allows for the synthesis of isolable organometallic Ni^II, Ni^III, and Ni^IV complexes. Illumination of the NiIV complex with blue LEDs results in rapid formation of the cyclic C-C product at room temperature.

Capturing All the Light: Panchromatic Visible Absorption with a Compact Architecture

Coupling two light absorbing pigments, a perylene and a porphyrin, into a dyad motif results in the unexpected ability to tune electronic structure of the chromophores and allows intense absorption of light spanning near-ultraviolet to near-infrared regions of the solar spectrum while maintaining a long excited-state lifetime and high fluorescence yield.

Amidine-Based Catalysts

This class of asymmetric catalysts developed by the Birman group shows remarkable efficacy and versatility in promoting enantioselective acylation reactions and related transformations. Their ease of preparation and flexibility of the catalyst design contribute to their growing popularity in the synthetic community.

The first example of C-C bond formation upon aerobic oxidation of a PdII complex

The tetradentate ligand ^tBuN4 facilitates the aerobic oxidation of organometallic Pd^II complexes by lowering their oxidation potential and stabilizing Pd^III and Pd^IV species, which undergo facile reductive elimination to generate C-C bond formation products. The study reported by the Mirica group suggests the possibility of using molecular oxygen as a green oxidant to promote the oxidative coupling of C-H bonds through transition metal catalysis.

Late First-Row Transition Metal Complexes of a Tetradentate Pyridinophane Ligand: Electronic Properties and Reactivity Implications

While previously the tetradentate ligand ^tBuN4 was shown to stabilize uncommon oxidation states such as Pd^III, the Mirica group has also shown that other uncommon oxidation states (e. g., Co^I, Ni^I, Cu^I, and Ni^III) can be accessed using this ligand system.

Electrophilic Addition to Azapentadienyl-Metal Complexes

Azapentadienyl-metal complexes possess two potential sites of reactivity for electrophiles, the nitrogen atom and the basic metal center. The Bleeke group has investigated the reactions of (1,2,3-η³)-(5-t-butylazapentadienyl)Rh(PMe₃)_x (x = 2 or 3) and (1,2,3-η³)-(5-t-butylazapentadienyl)Ir(PEt₃)_x (x = 2 or 3) with triflic acid and has shown that either the nitrogen atom or the metal center can serve as the primary reaction site (see accompanying graphic).

High-valent PdIII and PdIV intermediates in aerobically and photoinduced C-C bond formation reactions

High-valent Pd^III and Pd^IV species have been recently proposed as catalytically relevant intermediates in Pd-mediated C-C and C-heteroatom bond formation reactions. In this regard, the Mirica group has employed tetradentate ^RN4 ligands that allowed the unprecedented detection and characterization of both Pd^III and Pd^IV intermediates in aerobically and photoinduced C-C bond formation reactions. Read more here or

Native Electrospray Mass Spectrometry Reveals the Nature and Stoichiometry of Pigments in the FMO Photosynthetic Antenna Protein

The FMO antenna protein from green sulfur photosynthetic bacteria has been analyzed by native mass spectrometry by Wen et al. Biochemistry (2011) 50: 3502-3511. This revealed additional pigments that function to couple this complex to the chlorosome complex that feeds energy to it. This work was a collaboration between the Blankenship and Gross research groups.

Meet the Chemistry Department

Faculty, doctoral students and undergraduates talk about the department and their experiences at Washington University. From the outset, students get exposed to a broad range of expertise and fields. Interdisciplinary and collaborative research are strengths of this medium-sized department with considerable resources, instrumentation, and facilities.

Controlling the Surface of Microelectrode Arrays

Microelectrode arrays can be used to monitor in “real-time” binding events between small molecules and proteins. The result is unique opportunity to ascertain the effectiveness of chemical probes that target a given receptor. For this reason, the Moeller group is developing the synthetic and analytical chemistry needed to take full advantage of the arrays and then employing them in biological studies.