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X-WR-CALNAME;VALUE=TEXT:Professor Jeremy Smith (Indiana University)
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SUMMARY:Professor Jeremy Smith (Indiana University)
DESCRIPTION:<p>	<strong>New Catalysis Enabled by a Metal-Imido Ligand Cooperativity</strong></p><p>	 </p><span><span style="line-height:106%"><span>Significant work has established the utility of low-coordinate iron imido complexes in two-electron nitrene group transfer reactions. We have found that strongly donating bis(carbene)borates ligands expand the scope of iron imido chemistry, including new catalytic transformations that are redox neutral. In addition to providing a platform for accessing rare examples of isolable iron(V) and iron(VI) bis(imido) complexes, a three-coordinate iron(III) imido complex also serves as an entry point to the corresponding iron(II) imido. The high spin (<em>S</em> = 2) state of the iron(II) complex attenuates the iron-nitrogen multiple bond character, helping to create an unusually electrophilic imido ligand with reactivity patterns akin to those of early transition metals. In addition to known transformations such as such as [2+2] cycloadditions, the iron(II) imido is active in new reactions, including the first ene-like reactivity of an imido ligand. Many of these transformations form the basis for new catalytic reactions involving the cooperative action of iron and the imido ligand, including the catalytic </span></span></span><span><span style="line-height:106%"><span>a</span></span></span><span><span style="line-height:106%"><span>-deuteration of alkynes, the p<em>K</em><sub>a</sub>-dictated isomerization of alkenes and regioselective H/D exchange in pyridines.</span></span></span>
LOCATION:MIT
STATUS:CONFIRMED
DTSTART:20240313T201500Z
DTEND:20240313T211500Z
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