7th International Conference on Chemical Kinetics, MIT, 2011 A Laser Flash Photo

7th International Conference on Chemical Kinetics, MIT, 2011 A Laser Flash Photo www.phwiki.com

7th International Conference on Chemical Kinetics, MIT, 2011 A Laser Flash Photo

Puglise, Joe, Marketing Manager has reference to this Academic Journal, PHwiki organized this Journal 7th International Conference on Chemical Kinetics, MIT, 2011 A Laser Flash Photolysis Study of CO2 Reduction: Kinetics Leading to the Design of a Renewable Reducing Agent Outline of the Talk Computational in addition to experimental study of photochemical reduction of CO2 by Et3N. Use of the lessons learned in the design of a renewable amine. Future directions: Is an all-organic, renewable, visible- light photoreductant as long as CO2 possible Photochemical CO2 Reduction h

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The Key Idea Photochemical CO2 Reduction Matsuoka, S.; Kohzuki, T.; Pac, C.; Ishida, A.; Takamuku, S.; Kusaba, M.; Nakashima, N.; Yanagida, S., J. Phys. Chem. 1992, 96, 4437 h HCO2H PTP Fujiwara, H.; Kitamura, T.; Wada, Y.; Yanagida, S.; Kamat, P. V. J. Phys. Chem. 1999, 103, 4874. PTP – Photochemical CO2 Reduction

Effect of Ionization on C–H Reactivity Figures are H° in kcal/mol (exptl. + CBS–QB3) Computational Results PCM model as long as CH3CN These results from empirically corrected UB3LYP, calibrated against UMP2 in addition to UCCSD as long as smaller systems Later results use UCAM-B3LYP Hazardous system as long as common DFT functionals such as B3LYP, because of self-interaction error in radical ions in addition to long-range exchange error in CT states. J. Phys. Chem. A, 2007, 111, 3719 Self-Interaction Error in DFT: Bally, T.; Sastry, G. N. J. Phys. Chem. A, 1997, 101, 7923 Braieda, B.; Hiberty, P. C.; Savin, A. J. Phys. Chem. A, 1998, 102, 7872 Graefenstein, J.; Kraka, E.; Cremer, D. J. Chem. Phys. 2004, 120, 524 CAM-B3LYP: Yanai, T.; Tew, D. P.; H in addition to y, N. C. Chem. Phys. Lett. 2004, 393, 51. Reality Bites [1] : 0.35 [1] : 2.0 0.3 M CO2, 0.25M amine in CH3CN

Kanoufi, F.; Zu, Y.; Bard, A. J. J. Phys. Chem. B 2001, 105, 210. A Radical New Mechanism X Transient stability, at best. Radical cation would presumably be worse. Blocking C–H Reactivity Proton transfer CBS-QB3 Isodesmic Reactions H-atom transfer

X Transient stability, at best. Radical cation would presumably be worse. Stable to prolonged photolysis; af as long as ds no CO2 reduction. Blocking C–H Reactivity + PTP Generation of “PTP –” with the New Amine 440 nm 470 nm 285 nm 0 1 2 3 4 5 time / s + PTP Appearance quite different from that with Et3N Amine radical cation should have no b in addition to from 400 – 500nm Decay of “PTP –” is much faster than with Et3N Everything returns to baseline, whereas with Et3N it does not Decay of “PTP –” from the New Amine

Ion pair(s) The Ion-Pair Hypothesis Spectra taken after 500 ps. 10-4 M PTP, 1M NEt3 PTP – CO2 – Picosecond Infrared Studies Picosecond Infrared Studies 12CO2 – 13CO2 –

Spectra taken after 500 ps. 10-4 M PTP, 1M NEt3 PTP – CO2 – Picosecond Infrared Studies Prompt CO2 – as long as med by direct Et3N photo-ionization with 266 nm pump k1 k2 e–solv + Picosecond Infrared Studies Nanosecond Infrared Studies

Re-evaluation of the First Steps – – –10 kcal/mol [0] kcal/mol Re-evaluation of the First Steps – + CO2 Formate Production as f (PTP, ) 254 nm, no PTP 254 nm, sat. PTP >290 nm, sat. PTP >290 nm, no PTP 1 M Et3N in CH3CN

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What Have we Learned Electron addition to CO2 is difficult, in addition to probably doesn’t occur from PTP – except by “inner-sphere” carboxylation mechanism. BET to Et3N + can occur from both PTP – in addition to carboxylated PTP – in ion pairs Deprotonation of Et3N + blocks BET in addition to generates –amino radical –Amino radical seems to be necessary as long as CO2 reduction, but –Amino radical is also responsible as long as several of the byproducts H°trans = 414.6 – IP(amine) – PA(amine) (in kcal/mol) An Idea as long as the New Amine . J. Am. Chem. Soc. 2008, 130, 3169 Aliphatic amines ArNH2 ArNMe2 NH3 Sweet spot An Idea as long as the New Amine

An Idea as long as the New Amine Janovsky, I.; Knolle, W.; Naumov, S.; Williams, F. Chem. Eur. J. 2004, 10, 5524. e– Beam Freon + An Idea as long as the New Amine Synthesis in addition to Testing ~ 2x Et3N

An Unexpected Outcome Acknowledgments Rob Richardson Ed Holl in addition to Chris Stanley Claire Minton Mike George Sun Xue-Zhong James Calladine Charlotte Clark The Leverhulme Trust Royal Society/Wolfson Foundation

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