The Mirica group have used a tetradentate pyridonophane ligand containing a phenyl group to isolate several organometallic NiIII complexes and investigate their C-O bond formation reactivity. Interestingly, the NiIII-dihydroxide and NiIII-dimethoxide species can be synthesized and they undergo aryl methoxylation and hydroxylation that is favored by addition of an oxidant, which also depresses the β-hydride elimination side reaction.

The Hayes and Conradi groups are collaborating on in situ high-pressure high-temperature NMR to monitor the reaction of CO2 as it converts to magnesium carbonate and calcium carbonate.  This work involves WU's Consortium for Clean Coal Utilization

Read more in this special issue of Environmental Science & Technology: Surface et al. Environ. Sci. Technol., 2013, 47, 119?125. DOI: 10.1021/es301287n

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).

The photosynthetic megacomplex from a cyanobacterium, which scientists have managed to isolate in its complete, functioning form, weighs about 6 million Daltons. Bob Blankenship and Michael Gross collaborated on the research.

Alkaloid (–)-lobeline found in Indian tobacco (Lobelia inflata) is a potent nicotinomimetic that shows promise in the treatment of substance abuse. Hui Jiang and Ximin Li achieved a concise synthesis of this natural product via desymmetrization catalyzed by (S)-benzotetramisole (BTM), a versatile enantioselective acylation catalyst developed in the Birman group.

Now in its sixth year, “Catalysts for Change” brings St. Louis area 9th grade girls to campus for two weekends of immersion in science. Female chemistry graduate students develop and lead the activities, with General Chemistry lecturers and undergraduates assisting. Catalysts is sponsored by The Department of Chemistry, The Women’s Society, Women, Gender and Sexuality Studies, the Gephardt Institute, and The Teaching Center.

 

Determining Protein:Ligand Affinities by PLIMSTEX (Protein-Ligand Interactions by Mass Spectrometry, Titration, and H/D EXchange):

Using a new approach in mass spectrometry, the Michael Gross group follows amide exchange of a protein during titration with any ligand to give protein affinities. The curve, after modeling, yields the binding constant (Κi or βi)

Read more. . .

The Mirica group has recently reported that an organometallic PdII complex supported by the common tridentate ligand Me3tacn exhibits a very low oxidation potential and undergoes unprecedented rapid aerobic oxidation to generate a PdIV–OH complex. Thermolysis of the PdIV complex leads to selective formation of 2-tert-butylphenol.

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.

The Mirica group has reported that a PdII-dimethyl complex supported by the tridentate ligand Me3tacn undergoes rapid oxidation in the presence of O2 to produce a PdIV-trimethyl species. Upon thermolysis, reductive elimination occurs to generate a quantitative amount of ethane. This communication was features on the cover of Organometallics.

The image shows a "site-selective" reductive amination sequence on a microelectrode array, investigated by Kevin Moeller's group. In this experiment, Pd(II) is used at selected electrodes as an oxidant to generate a carbonyl for the reductive amination. Two reactions were conducted placing different fluorescent dyes on the array.