Chemical Society Seminar: Kit Cummins - Phosphorus-Element Bond-Forming Reactions


Maass Chemistry Building Room 10, 801 rue Sherbrooke Ouest, Montreal, QC, H3A 0B8, CA


Christopher “Kit” Colin Cummins benefited from formative undergraduate research experiences carried out sequentially in the laboratories of Professors Susan E. Kegley, James P. Collman, and Peter T. Wolczanski, respectively of Middlebury College, Stanford University and Cornell University. He graduated from the latter institution with an A.B. degree in 1989. Following this he undertook inorganic chemistry graduate studies under the direction of Professor Richard R. Schrock at the Massachusetts Institute of Technology, from which he obtained his Ph.D. degree in 1993 with a thesis entitled “Synthetic Investigations Featuring Amidometallic Complexes”. Also in 1993 Kit joined the chemistry faculty at MIT as an Assistant Professor; in 1996 he was promoted to the rank of Professor, and in 2015 he was named the Henry Dreyfus Professor of Chemistry.

Research themes in the Cummins group showcase exploratory synthesis and reactivity studies. General areas of interest include transition-metal coordination chemistry, organometallic chemistry, small molecule activation, metal-ligand multiple bonds, and group transfer reactions. We are developing anthracene-based molecular precursors to novel reactive intermediates and potential interstellar molecules. Such anthracene-based precursors are also of interest as group transfer reagents with applications in synthesis. We are in pursuit of reagents for selective chemical polyphosphorylation. Reactions of relevance to phosphorus sustainability are under development with the goal of minimizing waste and energy consumption in the upgrading of phosphate raw materials to value-added chemicals.

The research accomplishments of Kit’s group have been recognized with Harvard University’s E. Bright Wilson Prize, the Phi Lambda Upsilon National Fresenius Award, a Packard Fellowship for Science and Engineering, an Alfred P. Sloan Foundation Fellowship, the ACS Award in Pure Chemistry, the NSF Alan T. Waterman Award, the TR100 Award, an Alexander von Humboldt Research Award, the Dannie-Heineman Preis of the Akademie der Wissenschaften zu Göttingen, the ACS F. Albert Cotton Award in Synthetic Inorganic Chemistry, the Raymond and Beverly Sackler Prize in the Physical Sciences, the inaugural Inorganic Chemistry Lectureship Award, the RSC Ludwig Mond Award, and the Linus Pauling medal. Kit has been a Fellow of the Hagler Institute for Advanced Study at Texas A&M University, he is a corresponding member of the Akademie der Wissenschaften zu Göttingen, an honorary member of the Israel Chemical Society, and an elected member of both the American Academy of Arts and Sciences and the National Academy of Sciences.


Reactive Intermediates & Group Transfer Reactions. We design and synthesize molecular precursors that can be activated by a stimulus to release a small molecule of interest. The molecular precursors themselves are isolated as crystalline solids; they are typically soluble in common organic solvents and can be weighed out and used as needed. For example, the molecule P2A2 (A = anthracene or C14H10) is a molecular precursor to the diatomic molecule P2. Compounds having the formula RPA serve to transfer the phosphinidene (PR) group either as a freely diffusing species (R = NR’2, singlet phosphinidene) or else by inner sphere mechanisms (R = alkyl, triplet phosphinidene). Using the RPA reagents we are developing reactions analogous to cyclopropanation and aziridination for delivery of the PR group to olefins with the formation of three-membered P-containing rings, phosphiranes.

Metaphosphates and Phosphorylating Methodology. Crystalline metaphosphate salts with lipophilic counter cations are useful starting materials applicable in polar organic media. “Metaphosphate” refers to the inorganic ion PO3(-)which, unlike its chemical cousin, nitrate, exists not as a monomeric species but rather as oligomeric rings: [(PO3)n]n-. These cyclic phosphates can be converted into electrophilic phosphorylating agents (a) by treatment with peptide coupling reagents, or (b) by conversion into their crystalline acid forms and subsequent dehydration. Such activated cyclic phosphates can be used directly for oligophosphorylation of C, N, and O nucleophiles. Phosphorylation of the Wittig reagent leads to a new phosphorus ylide with a cyclic phosphate as the C-substituent and a non-hydrolyzable P-C bond, allowing for conjugation of oligophosphate groups to a biomolecule of interest by aldehyde olefination.

Sustainable Phosphorus Chemistry. The industrial “thermal process” by which the raw material phosphate rock is upgraded to white phosphorus is energy intensive and generates CO2. We seek alternative chemical routes to value-added P-chemicals from phosphate starting materials obtained either by the agricultural “wet process” or by phosphorus recovery and recycling from waste streams. Trichlorosilane is a high production volume chemical for its use in the manufacture of silicon for solar panels. We show that trichlorosilane is a reductant for phosphate raw materials leading to the bis(trichlorosilyl) phosphide anion [P(SiCl3)2]- as a versatile intermediate en route to compounds containing P-C bonds.


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Tomislav Friscic
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