Supporting Information. Why is there no in-plane proton-coupled electron transfer from. A theoretical and experimental investigation

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1 Electronic Supplementry Mteril (ESI) for Photochemicl & Photobiologicl Sciences This journl is (c) The Royl Society of Chemistry nd wner Societies 2010 Supporting Informtion Why is there no in-plne proton-coupled electron trnsfer from ryloxy rdicls? A theoreticl nd experimentl investigtion Yu-Zhe Chen, Yonghui Tin, Miklos Kertesz, Richrd G. Weiss* Deprtment of Chemistry, Georgetown University, Wshington, DC, , USA. Emil: weissr@georgetown.edu This section contins: -Synthetic scheme to 5 -Representtive HPLC chromtogrm -Computed totl energies nd thermochemicl prmeters. -Computed rte constnts by Eyring s eqution. -Loclized orbitls nd SMs of the TSs for compounds 2,3,5 nd 6. -Detils of tunneling rte constnt clcultions. -Complete list of uthors for ref )NH 4 H HCl Pyridine NH 1) NH 2) p-toluene sulfonyl chloride 2) NN 2, H 2 S 4 MgBr -10 o C Ph Ph H H Ph CCH 3 CF 3 CH (CH 3 C) 2 benzene NBH 4 5 Scheme S1. Synthetic scheme for 5 1

2 Electronic Supplementry Mteril (ESI) for Photochemicl & Photobiologicl Sciences This journl is (c) The Royl Society of Chemistry nd wner Societies 2010 Figure S1. Representtive HPLC chromtogrm fter irrdition of 5. Detector wvelength = 330 nm. See text for detils. Tble S1. Clculted thermochemistry vlues from Gussin03 for the IHT process t the UB3LYP/6-31 G*// UB3LYP/6-31 G* level H sum G sum H corr G corr H sum +H corr G sum +G corr S b b TS b TS b TS

3 Electronic Supplementry Mteril (ESI) for Photochemicl & Photobiologicl Sciences This journl is (c) The Royl Society of Chemistry nd wner Societies b TS b TS b TS Hrtree/prticle b. cl mol -1 K -1 Tble S2. Totl energy prmeters for the intrmoleculr hydrogen trnsfer within ryloxy rdicls 1-6. Rdicls ΔH rxn ΔH ΔS rxn b ΔS b ΔG rxn ΔG from kcl mol -1 ; b. cl mol -1 K -1. Tble S3. Clculted IHT rection rte constnts (k) for 1-6 t 300K, 400K nd 500K using eq 1 in the min text. k (s -1 ) Temperture K K K

4 Electronic Supplementry Mteril (ESI) for Photochemicl & Photobiologicl Sciences This journl is (c) The Royl Society of Chemistry nd wner Societies : 3: 4

5 Electronic Supplementry Mteril (ESI) for Photochemicl & Photobiologicl Sciences This journl is (c) The Royl Society of Chemistry nd wner Societies : 6: Figure S2. Pipek-Mezey loclized orbitls of the trnsition stte structures of 2, 3, 5 nd 6. 5

6 Electronic Supplementry Mteril (ESI) for Photochemicl & Photobiologicl Sciences This journl is (c) The Royl Society of Chemistry nd wner Societies Figure S3. SMs of the trnsition stte structures of 2, 3, 5, 6. Estimtes of tunneling rte constnts bsed on eq. (2) nd (3) of Cmpos et l. 1 S2 below). (eqs S1 nd k ZPE G = cν P ( EZPE ) (S1) C H P G ( E ZPE ) = 1/(1 + exp{[1/ c ν ] ΔE }) (S2) The quntities re defined s: c = speed of light; ν C H = frequency for typicl C-H vibrtion; k ZPE = rte of tunneling from zero point energy (ZPE) levels; P G = quntum mechnicl permebility of the brrier (ssumed to be qudrtic with n imginry frequency t the brrier top of ν ). The brrier from the rectnts, not including ZPE = ΔE. The ssumed numericl vlue ws c ν C H. s Tble S4. Clculted IHT tunneling rection rte constnts (k ZPE ) for 1-6 using eqs S1 nd S2. ΔE [kcl/mol] ν [cm -1 ] P G k ZPE (s -1 ) E E E E E E E E E E E E+04 6

7 Electronic Supplementry Mteril (ESI) for Photochemicl & Photobiologicl Sciences This journl is (c) The Royl Society of Chemistry nd wner Societies 2010 Complete list of uthors for ref. 19 (min text). Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseri, G. E.; Robb, M. A.; Cheesemn, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burnt, J. C.; Millm, J. M.; Iyengr, S. S.; Tomsi, J.; Brone, V.; Mennucci, B.; Cossi, M.; Sclmni, G.; Reg, N.; Petersson, G. A.; Nktsuji, H.; Hd, M.; Ehr, M.; Toyot, K.; Fukud, R.; Hsegw, J.; Ishid, M.; Nkjim, T.; Hond, Y.; Kito,.; Nki, H.; Klene, M.; Li, X.; Knox, J. E.; Hrtchin, H. P.; Cross, J. B.; Bkken, V.; Admo, C.; Jrmillo, J.; Gomperts, R.; Strtmnn, R. E.; Yzyev,.; Austin, A. J.; Cmmi, R.; Pomelli, C.; chterski, J. W.; Ayl, P. Y.; Morokum, K.; Voth, G. A.; Slvdor, P.; Dnnenberg, J. J.; Zkrzewski, V. G.; Dpprich, S.; Dniels, A. D.; Strin, M. C.; Frks,.; Mlick, D. K.; Rbuck, A. D.; Rghvchri, K.; Foresmn, J. B.; rtiz, J. V.; Cui, Q.; Bboul, A. G.; Clifford, S.; Cioslowski, J.; Stefnov, B. B.; Liu, G.; Lishenko, A.; Piskorz, P.; Komromi, I.; Mrtin, R. L.; Fox, D. J.; Keith, T.; Al-Lhm, M. A.; Peng, C. Y.; Nnykkr, A.; Chllcombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzlez, C.; Pople, J. A. Gussin 03, revision B.04; Gussin, Inc.: Wllingford, CT, L. M. Cmpos, M. V. Wrrier, K. Peterfy, K. N. Houk, M. A. Grci-Griby, Secondry Alph Isotope Effects on Deuterium Tunneling in Triplet o-methylnthrones: Extrordinry Sensitivity to Brrier Width. J. Am. Chem. Soc. 2005, 127,