Carbon Dioxide Capture and Functionalization from a Molecular Ti(III) Oxo Anion
Abstract
AbstractCarbon dioxide capture and functionalization sequesters carbon dioxide in more robust products and offers a viable route to reducing greenhouse gas emissions. We present herein a unique molecular TiIII oxo anion that reversibly binds CO2 to allow both its sequestration and functionalization. The reduction of [(PN)2Ti═O] (1) [PN = (2‐PiiPr2‐4‐methylphenyl)(mesityl)amide] with KC8 and 2.2.2‐cryptand (crypt) resulted in formation of [K(crypt)][(PN)2Ti═O] (2), which was fully characterized and shown to contain a Ti‐centered radical. Complex 2 reacts with Al(CH3)3 to form [K(crypt)][(PN)2Ti{O(Al(CH3)3}] (3), which can be independently prepared from [K(crypt)][(PN)2Ti(OCP)] and Al(CH3)3. Whereas 1 does not react with CO2, 2 rapidly captures the gas (1 atm, 25 °C) to produce a TiIII carbonate [K(crypt)][(PN)2Ti(κ2‐O2C═O)] (4). Chemical and electrochemical oxidation of 4 releases CO2 to regenerate 1 while a soluble organic carbonate [Me3SiOC(O)OSiMe3, Me = CH3] is obtained from reaction of 4 with ClSiMe3.
Article Details
Authors (10)
Samuel S. Veroneau
Department of Chemistry University of Pennsylvania 231 S. 34<sup>th</sup> Street Philadelphia PA 19104 USA
Jacob S. Mohar
Department of Chemistry, University of Pennsylvania, 231 S. 34th St., Philadelphia, Pennsylvania 19104, United States
Mrinal Bhunia
Department of Chemistry, University of Pennsylvania, 231 S. 34th St., Philadelphia, Pennsylvania 19104, United States
Hannah Farber
Department of Chemistry University of Pennsylvania 231 S. 34<sup>th</sup> Street Philadelphia PA 19104 USA
Alexander L. Laughlin
Department of Chemistry and Chemical Biology, Baker Laboratory
Robert W. Voland
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University
Alexandra Bacon
Department of Chemistry University of Pennsylvania 231 S. 34<sup>th</sup> Street Philadelphia PA 19104 USA
Michael R. Gau
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry
Kyle M. Lancaster
Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, 162 Sciences Drive, Ithaca, New York 14853, United States
Daniel J. Mindiola
Department of Chemistry, University of Pennsylvania, 231 S. 34th St., Philadelphia, Pennsylvania 19104, United States