Slow hydrogen atom transfer reactions of oxo- and hydroxo-vanadium compounds: The importance of intrinsic barriers

Journal of the American Chemical Society

Volumn 131, Issue 13, 2009, Pages 4729-4743

  Waidmann, Christopher R ^a,b   Zhou, Xin ^a,b   Tsai, Erin A ^a,b   Kaminsky, Werner ^a,b,c   Hrovat, David A ^a,b   Borden, Weston Thatcher ^a,b   Mayer, James M ^a,b  

^a UNIVERSITY OF WASHINGTON   (United States)

^b UNIVERSITY OF NORTH TEXAS   (United States)

^c University of Washington crystallographic facility   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ATOMS; EQUILIBRIUM CONSTANTS; FREE RADICAL REACTIONS; HYDROGEN; KETONES; LABELS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PHENOLS; POLYCYCLIC AROMATIC HYDROCARBONS; RATE CONSTANTS; RUTHENIUM; RUTHENIUM COMPOUNDS; SULFUR COMPOUNDS; VANADIUM ALLOYS;

AMBIENT TEMPERATURES; BARRIER HEIGHTS; BENZOQUINONE; BIPYRIDINE; BOND STRENGTH; C-H BOND; DFT CALCULATION; DIHYDROANTHRACENE; H NMR SPECTRA; H-BONDS; HYDROGEN ATOMS; HYDROGEN-ATOM TRANSFER; HYDROXO COMPLEXES; INTRINSIC BARRIERS; MARCUS CROSS-RELATIONS; ORBITAL OCCUPANCY; ORGANIC SUBSTRATE; RUTHENIUM COMPLEXES; SELF-EXCHANGE; SELF-EXCHANGE REACTIONS; STRUCTURAL REORGANIZATION; TETRAMETHYL; VANADIUM COMPLEXES;

VANADIUM COMPOUNDS;

HYDROGEN; VANADIUM DERIVATIVE; RUTHENIUM DERIVATIVE;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; NUCLEAR MAGNETIC RESONANCE; OXIDATION; PROTON TRANSPORT; TEMPERATURE SENSITIVE CLONE; CHEMISTRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OXIDATION REDUCTION REACTION; QUANTUM THEORY;

HYDROGEN; MAGNETIC RESONANCE SPECTROSCOPY; OXIDATION-REDUCTION; QUANTUM THEORY; RUTHENIUM COMPOUNDS; VANADIUM COMPOUNDS;

EID: 67749118152     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja808698x     Document Type: Article

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163. E1/2 for TEMPOH0/+· in MeCN is 0.71 ( 0.02 V (converted from Ag/AgNO3 to FeCp2 0/+ by subtracting 0.088 V): Semmelhack, M. F.; Chou, C. S.; Cortes, D. A J. Am. Chem. Soc. 1983, 105, 4492-4494.
164. Irreversible oxidation of hydroquinone in MeCN occurs at 0.73 V (converted from SCE to FeCp2 0/+ by subtracting 0.40 V): Parker, V. D. J. Chem. Soc., Chem. Commun. 1969, 716-717.
165. Bordwell, F. G.; Liu, W. Z. J. Am. Chem. Soc. 1996, 118, 10819- 10823.
166. (a) The pKa values of xanthene and dihydroanthracene are reported as 30.1 in: Bordwell, F. G.; Cheng, J.; Ji, G.; Satish, A. V.; Zhang, X, J. Am. Chem. Soc. 1991, 113, 9790-9795.
167. (b) The above pKa's in DMSO can be converted to a pKa in CH3CN following: Wayner, D. D. M.; Parker, V. D. Acc. Chem. Res. 1993, 26, 287-294.
168. Wagner, P. J.; Zhang, Y.; Puchalski, A. E. J. Phys. Chem. 1993, 97, 13368-13374.
169. (a) Iordanova, N.; Decornez, H.; Hammes-Schiffer, S. J. Am. Chem. Soc. 2001, 123, 3723-3733.
170. (b) Hammes-Schiffer, S. Acc. Chem. Res. 2001, 34, 273-281.
171. (c) Hatcher, E.; Soudackov, A.; Hammes-Schiffer, S J. Phys. Chem. B 2005, 109, 18565-18574.
172. (a) Benson, S. W. Thermochemical Kinetics, 2nd ed.; Wiley: New York, 1976.
173. (b) Foti, M.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1994, 116, 9440-9447.
174. See, for instance, discussions in refs 46b, 79, 95, and 96.
175. Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265- 322.
176. fxy 82 is usually close to 1.
177. Mader, E. A.; Mayer, J. M. Submitted for publication.
178. Eberson, L. Electron Transfer Reactions in Organic Chemistry; Springer-Verlag: Berlin/Heidelberg, 1987; Chapter 3.
179. Wu, A.; Datta, A.; Hrovat, D. A.; Borden, W. T.; Mayer, J. M., manuscript in preparation.
180. Bryant, J. R. Ph. D. Thesis; University of Washington: Seattle, WA, December 2002.
181. Warren, J. J.; Mayer, J. M. Manuscript in preparation.
182. (a) We also performed calculations with the MPW1K functional.89b The energies for all of the steps in Figure 8 computed with MPW1K/ 6-31+G(d,p) were similar to those computed with B3LYP/6-31G(d), except for the hydrogen-transfer step (cfd). The MPW1K calculations gave values about 10 kcal mol-1 higher for the vanadium complex and 7-8 kcal mol-1 higher for the ruthenium complexes. The barrier heights computed with MPW1K were higher than B3LYP values by 12.8 kcal mol-1 for VO2/V(O)OH and by 11.6 and 10.4 kcal mol-1 for RuO(pyrr)/Ru(OH)(pyrr) and RuO(F)/Ru(OH)(F), respectively. Probably through a fortuitous cancellation of errors, the B3LYP barrier heights are in much better agreement with experiment than are the MPW1K barrier heights.
183. (b) Lynch, B. J.; Fast, P. L.; Harris, M.; Truhlar, D. G. J. Phys. Chem. A 2000, 104, 4811.
184. The V-OH bond of 1c is ∼0.2 Å shorter than a typical RuIII-OH bond [a structure of RuIIIOH(bpy)2(py)2+ has not been reported]: (a) Man, M. L.; Zhu, J.; Ng, S. M.; Zhou, Z.; Yin, C.; Lin, Z.; Lau, C. P. Organometallics 2004, 23, 6214-6220.
185. (b) Jitsukawa, K.; Oka, Y.; Yamaguchi, S.; Masuda, H. Inorg. Chem. 2004, 43, 8119-8129.
186. (c) Takahashi, Y.; Hikichi, S.; Moro-oka, Y.; Akita, M. Polyhedron 2004, 23, 225-234.
187. (d) Nagao, H.; Aoyagi, K.; Yukawa, Y.; Howell, F. S.; Mukaida, M.; Kakihana, H. Bull. Chem. Soc. Jpn. 1987, 60, 3247- 3245.
188. (e) Gibson, D. H.; Pariya, C.; Mashuta, M. S. Organometallics 2004, 23, 2510-2513.
189. (f) Gemel, C.; Mereiter, K.; Schmid, R.; Kirchner, K. Organometallics 1997, 16, 5601-5603.
190. (g) Schneider, R.; Weybermüller, T.; Wieghardt, K. Inorg. Chem. 1993, 32, 4925- 4934.
191. (h) Anderson, C.; Beauchamp, A. L. Inorg. Chem. 1995, 34, 6065-6073.
192. VdO bonds62 are ca. 0.16 Å shorter than corresponding RuIVdO bonds [a structure of RuIVO(bpy)2(py)2+ has not been reported]: (a) Che, C.; Lai, T.; Wong, K. Inorg. Chem. 1987, 26, 2289-229, and references therein.
193. (b) Che, C.; Tang, W.; Lee, W.; Wong, W.; Lai, T. J. Chem. Soc., Dalton Trans. 1989, 2011-2016.
194. (c) Wong, K.; Che, C.; Yip, W.; Wang, R.; Mak, T. C. W. J. Chem. Soc., Dalton Trans. 1992, 1417-1421.
195. (a) Moyer, B. A.; Meyer, T. J. J. Am. Chem. Soc. 1978, 100, 3601- 3603.
196. (b) Aoyagi, K.; Yukawa, Y.; Shimuzu, K.; Mukaida, M.; Takeuchi, T.; Kakihana, H. Bull. Chem. Soc. Jpn. 1986, 59, 1493- 1499.
197. (c) Marmion, M. E.; Takeuchi, K. J. J. Am. Chem. Soc. 1986, 108, 510-511.
198. In a three-electron π bond, the electron that occupies the antibonding orbital more than cancels the bonding contributed by one of the electrons in the bonding orbital. See, for example: Jorgensen, W. L.; Borden, W. T J. Am. Chem. Soc. 1973, 95, 6649.
199. (a) Binstead, R. A.; McGuire, M. E.; Dovletoglou, A.; Seok, W. K.; Roecker, L. E.; Meyer, T. J. J. Am. Chem. Soc. 1992, 114, 173-186.
200. (b) See also ref 1.
201. (a) Mayer, J. M.; Hrovat, D. A.; Thomas, J. L.; Borden, W. T. J. Am. Chem. Soc. 2002, 124, 11142-11147.
202. (b) Lingwood, M.; Hammond, J. R.; Hrovat, D. A.; Mayer, J. M.; Borden, W. T. J. Chem. Theory Comput. 2006, 2, 740-745.
203. Tishchenko, O.; Truhlar, D. G.; Ceulemans, A.; Nguyen, M. T. J. Am. Chem. Soc. 2008, 130, 7000-7010.
204. Binstead, R. A.; Meyer, T. J. J. Am. Chem. Soc. 1987, 109, 3287- 3297, The emphasis is in the original. This definition of HAT precedes Meyer's different definition (quoted above) in refs 1 and 94.
205. http://www.glasscontoursolventsystems.com/index.php/about.
206. Modarelli, D. A.; Rossitto, F. C.; Lahti, P. M. Tetrahedron Lett. 1989, 30, 4473-4476.