Using picosecond and nanosecond time-resolved infrared spectroscopy for the investigation of excited states and reaction intermediates of inorganic systems

Journal of the Chemical Society. Dalton Transactions

Volumn 3, Issue 21, 2003, Pages 3996-4006

  Kuimova, Marina K ^a   Alsindi, Wassim Z ^a   Dyer, Joanne ^a   Grills, David C ^a   Jina, Omar S ^a   Matousek, Pavel ^b   Parker, Anthony W ^b   Portius, Peter ^a   Zhong Sun, Xue ^a   Towrie, Michael ^b   Wilson, Claire ^a   Yang, Jixin ^a   George, Michael W ^a  

^a UNIVERSITY OF NOTTINGHAM   (United Kingdom)

^b Harwell Science and Innovation Campus   (United Kingdom)

Author keywords

Chromiun; Kinetics; Photochemistry, photophysics; Rhenium; Vibrational spectroscopy

Indexed keywords

ABSORPTION; INFRARED SPECTROSCOPY; PHOTOCHEMICAL REACTIONS; PHOTOLYSIS; RAMAN SPECTROSCOPY; REACTION KINETICS; ULTRAVIOLET RADIATION;

DICHLORODIPYRIDOPHENAZINE; EXCITED STATES; FLASH PHOTOLYSIS; INORGANIC SYSTEMS; TIME RESOLVED INFRARED SPECTROSCOPY;

ORGANOMETALLICS;

EID: 0242695595     PISSN: 14779226     EISSN: None     Source Type: Journal    
DOI: 10.1039/b306303h     Document Type: Article

References (152)

1. R.G.W. Norrish, G. Porter: Nature (London) (1949), 164: 658.
2. D.C. Grills and M.W. George, Fast and Ultrafast Time-resolved Mid-infrared Spectrometry Using Lasers, in Handbook of Vibrational Spectroscopy, ed. J.M. Chalmers and P.R. Griffiths, John Wiley & Sons Ltd., Chichester, (2002), vol. 1:, p. 677.
3. R. Wilbrandt: Biospectroscopy (1996), 2: 263.
4. K.N. Tanner, R.L. King: Nature (1958), 181: 963.
5. G.C. Pimentel, K.C. Herr: J. Chim. Phys. (1964), 61: 1509.
6. K.C. Herr, G.C. Pimentel: Appl. Opt. (1965), 4: 25.
7. A.S. Lefohn, G.C. Pimentel: J. Chem. Phys. (1971), 55: 1213.
8. L.Y. Tan, A.M. Winer, G.C. Pimentel: J. Chem. Phys. (1972), 57: 4028.
9. F. Siebert, W. Mäntele, W. Kreutz: Biophys. Struct. Mech. (1980), 6: 139.
10. H. Hermann, F.W. Grevels, A. Henne, K. Schaffner: J. Phys. Chem. (1982), 86: 5151.
11. S.P. Church, F.W. Grevels, H. Hermann, K. Schaffner: Inorg. Chem. (1984), 23: 3830.
12. S.P. Church, H. Hermann, F.W. Grevels, K. Schaffner: J. Chem. Soc., Chem. Commun. (1984), 785.
13. T.R. Fletcher, R.N. Rosenfeld: J. Am. Chem. Soc. (1983), 105: 6358.
14. A.J. Ouderkirk, P. Wermer, N.L. Schultz, E. Weitz: J. Am. Chem. Soc. (1983), 105: 3354.
15. B.D. Moore, M.B. Simpson, M. Poliakoff, J.J. Turner: J. Chem. Soc., Chem. Commun. (1984), 972.
16. M.W. George, M. Poliakoff, J.J. Turner: Analyst (1994), 119: 551.
17. X.Z. Sun, S.M. Nikiforov, J. Yang, C.S. Colley, M.W. George: Appl. Spectrosc. (2002), 56: 31.
18. G.D. Smith and R.A. Palmer, Fast Time-resolved Mid-infrared Spectroscopy Using an Interferometer, in Handbook of Vibrational Spectroscopy, ed. J.M. Chalmers and P.R. Griffiths, John Wiley & Sons Ltd., (2002), vol. 1:, p. 625.
19. A. Laubereau, W. Kaiser: Rev. Mod. Phys. (1978), 50: 607.
20. P. Hamm, M. Lim, R.M. Hochstrasser: J. Chem. Phys. (1997), 107: 10523.
21. Y. Wang, J.B. Asbury, T. Lian: J. Phys. Chem. A (2000), 104: 4291.
22. M. Towrie, D.C. Grills, J. Dyer, J.A. Weinstein, P. Matousek, R. Barton, P.D. Bailey, N. Subramaniam, W.M. Kwok, C. Ma, D. Phillips, A.W. Parker, M.W. George: Appl. Spectrosc. (2003), 57: 367.
23. S.M. Arrivo, V.D. Kleiman, T.P. Dougherty, E.J. Heilweil: Opt. Lett. (1997), 22: 1488.
24. P.T. Snee, H. Yang, K.T. Kotz, C.K. Payne, C.B. Harris: J. Phys. Chem. A (1999), 103: 10426.
25. H.D. Stoeffler, N.B. Thornton, S.L. Temkin, K.S. Schanze: J. Am. Chem. Soc. (1995), 117: 7119.
26. M. Poliakoff, S.M. Howdle, S.G. Kazarian: Angew. Chem., Int. Ed. Engl. (1995), 34: 1275.
27. Organic and Inorganic Photochemistry, ed. V. Ramamurthy and K.S. Schanze, Marcel Dekker, New York, (1998).
28. R. Ballardini, V. Balzani, A. Credi, M.T. Gandolfi, M. Venturi: Acc. Chem. Res. (2001), 34: 445.
29. J.K. Lee, D.S. Yoo, E.S. Handy, M.F. Rubner: Appl. Phys. Lett. (1996), 69: 1686.
30. D.F. O’Brien, M.A. Baldo, M.E. Thompson, S.R. Forrest: Appl. Phys. Lett. (1999), 74: 442.
31. B. O’Regan, M. Gratzel: Nature (1991), 353: 737.
32. P.G. Bradley, N. Kress, B.A. Hornberger, R.F. Dallinger, W.H. Woodruff: J. Am. Chem. Soc. (1981), 103: 7441.
33. M.W. George, J.J. Turner: Coord. Chem. Rev. (1998), 177: 201.
34. J.R. Schoonover, G.F. Strouse, K.M. Omberg, R.B. Dyer: Comments Inorg. Chem. (1996), 18: 165.
35. J.R. Schoonover, G.F. Strouse: Chem. Rev. (1998), 98: 1335.
36. J.R. Schoonover, G.F. Strouse, R.B. Dyer, W.D. Bates, P.Y. Chen, T.J. Meyer: Inorg. Chem. (1996), 35: 273.
37. H.A. Nieuwenhuis, D.J. Stufkens, R.A. McNicholl, A.H.R. Alobaidi, C.G. Coates, S.E.J. Bell, J.J. McGarvey, J. Westwell, M.W. George, J.J. Turner: J. Am. Chem. Soc. (1995), 117: 5579.
38. J.A. Weinstein, J. van Slageren, D.J. Stufkens, S. Zalis, M.W. George: J. Chem. Soc., Dalton Trans. (2001), 2587.
39. B.D. Rossenaar, M.W. George, F.P.A. Johnson, D.J. Stufkens, J.J. Turner, A. Vlcek Jr.: J. Am. Chem. Soc. (1995), 117: 11582.
40. K.A. Walters, D.M. Dattelbaum, K.D. Ley, J.R. Schoonover, T.J. Meyer, K.S. Schanze: Chem. Commun. (2001), 1834.
41. S. Záliš, I.R. Farrell, A. Vlcek Jr.: J. Am. Chem. Soc. (2003), 125: 4580.
42. I.R. Farrell, P. Matousek, M. Towrie, A.W. Parker, D.C. Grills, M.W. George, A. Vlcek Jr.: Inorg. Chem. (2002), 41: 4318.
43. A. Vlcek Jr., I.R. Farrell, D.J. Liard, P. Matousek, M. Towrie, A.W. Parker, D.C. Grills, M.W. George: J. Chem. Soc., Dalton Trans. (2002), 701.
44. R.A. Palmer, G.L. Edwards, M.S. Hutson and A.G. Taube, Abstracts of Pittcon 2003, Orlando, Florida, (2003), p. 549, 1600-3.
45. F.P.A. Johnson, M.W. George, S.L. Morrison, J.J. Turner: J. Chem. Soc., Chem. Commun. (1995), 391.
46. E.L. Patrick, C.J. Ray, G.D. Meyer, T.P. Ortiz, J.A. Marshall, J.A. Brozik, M.A. Summers, J.W. Kenney III: J. Am. Chem. Soc. (2003), 125: 5461.
47. P.Y. Chen, K.M. Omberg, D.A. Kavaliunas, J.A. Treadway, R.A. Palmer, T.J. Meyer: Inorg. Chem. (1997), 36: 954.
48. P.Y. Chen, R.A. Palmer, T.J. Meyer: J. Phys.Chem. A (1998), 102: 3042.
49. K.M. Omberg, G.D. Smith, D.A. Kavaliunas, P.Y. Chen, J.A. Treadway, J.R. Schoonover, R.A. Palmer, T.J. Meyer: Inorg. Chem. (1999), 38: 951.
50. J.A. Weinstein, D.C. Grills, M. Towrie, P. Matousek, A.W. Parker, M.W. George: Chem. Commun. (2002), 382.
51. A.E. Curtright, J.K. McCusker: J. Phys. Chem. A (1999), 103: 7032.
52. K.M. Omberg, J.R. Schoonover, S. Bernhard, J.A. Moss, J.A. Treadway, E.M. Kober, R.B. Dyer, T.J. Meyer: Inorg. Chem. (1998), 37: 3505.
53. K.M. Omberg, J.R. Schoonover, J.A. Treadway, R.M. Leasure, R.B. Dyer, T.J. Meyer: J. Am. Chem. Soc. (1997), 119: 7013.
54. K.E. Erkkila, D.T. Odom, J.K. Barton: Chem. Rev. (1999), 99: 2777.
55. N.J. Turro, J.K. Barton, D.A. Tomalia: Acc. Chem. Res. (1991), 24: 332.
56. J. Fees, W. Kaim, M. Moscherosch, W. Matheis, J. Klima, M. Krejcik, S. Zalis: Inorg. Chem. (1993), 32: 166.
57. J. Fees, M. Ketterle, A. Klein, J. Fiedler, W. Kaim: J. Chem. Soc., Dalton Trans. (1999), 2595.
58. E.J.C. Olson, D. Hu, A. Hormann, A.M. Jonkman, M.R. Arkin, E.D.A. Stemp, J.K. Barton, P.F. Barbara: J. Am. Chem. Soc. (1997), 119: 11458.
59. C.G. Coates, J. Olofsson, M. Coletti, J.J. McGarvey, B. Onfelt, P. Lincoln, B. Norden, E. Tuite, P. Matousek, A.W. Parker: J. Phys. Chem. B (2001), 105: 12653.
60. R.B. Nair, B.M. Cullum, C.J. Murphy: Inorg. Chem. (1997), 36: 962.
61. E. Sabatani, H.D. Nikol, H.B. Gray, F.C. Anson: J. Am. Chem. Soc. (1996), 118: 1158.
62. A.E. Friedman, J.C. Chambron, J.P. Sauvage, N.J. Turro, J.K. Barton: J. Am. Chem. Soc. (1990), 112: 4960.
63. R.E. Holmlin, J.K. Barton: Inorg. Chem. (1995), 34: 7.
64. R.E. Holmlin, J.A. Yao, J.K. Barton: Inorg. Chem. (1999), 38: 174.
65. M.K. Brennaman, J.H. Alstrum-Acevedo, C.N. Fleming, P. Jang, T.J. Meyer, J.M. Papanikolas: J. Am. Chem. Soc. (2002), 124: 15094.
66. B. Onfelt, J. Olofsson, P. Lincoln, B. Norden: J. Phys. Chem. A (2003), 107: 1000.
67. C.G. Coates, L. Jacquet, J.J. McGarvey, S.E.J. Bell, A.H.R. AlObaidi, J.M. Kelly: J. Am. Chem. Soc. (1997), 119: 7130.
68. M.R. Waterland, K.C. Gordon, J.J. McGarvey, P.M. Jayaweera: J. Chem. Soc., Dalton Trans. (1998), 609.
69. J. Olofsson, B. Onfelt, P. Lincoln, B. Norden, P. Matousek, A.W. Parker, E. Tuite: J. Inorg. Biochem. (2002), 91: 286.
70. C.G. Coates, P. Callaghan, J.J. McGarvey, J.M. Kelly, L. Jacquet, A. Kirsch-De Mesmaeker: J. Mol. Struct. (2001), 598: 15.
71. J. Dyer, W.J. Blau, C.G. Coates, C.M. Creely, J.D. Gavey, M.W. George, D.C. Grills, S. Hudson, J.M. Kelly, P. Matousek, J.J. McGarvey, J. McMaster, A.W. Parker, M. Towrie, J.A. Weinstein: Photochem. Photobiol. Sci. (2003), 2: 542.
72. E. Amouyal, A. Homsi, J.C. Chambron, J.P. Sauvage: J. Chem. Soc., Dalton Trans. (1990), 1841.
73. A.C. Bhasikuttan, M. Suzuki, S. Nakashima, T. Okada: J. Am. Chem. Soc. (2002), 124: 8398.
74. T.P. Dougherty, E.J. Heilweil: Chem. Phys. Lett. (1994), 227: 19.
75. T.P. Dougherty, E.J. Heilweil: J. Chem. Phys. (1994), 100: 4006.
76. J.B. Asbury, H.N. Ghosh, J.S. Yeston, R.G. Bergman, T.Q. Lian: Organometallics (1998), 17: 3417.
77. T. Lian, S.E. Bromberg, H. Yang, G. Proulx, R.G. Bergman, C.B. Harris: J. Am. Chem. Soc. (1996), 118: 3769.
78. E. Weitz: J. Phys. Chem. (1994), 98: 11256.
79. K. McFarlane, B. Lee, J. Bridgewater, P.C. Ford: J. Organomet. Chem. (1998), 554: 49.
80. M. Poliakoff, E. Weitz: Adv. Organomet. Chem. (1986), 25: 277.
81. X.Z. Sun, M.W. George, S.G. Kazarian, S.M. Nikiforov, M. Poliakoff: J. Am. Chem. Soc. (1996), 118: 10525.
82. H. Sun, H. Frei: J. Phys. Chem. B (1997), 101: 205.
83. J.B. Asbury, E. Hao, Y.Q. Wang, H.N. Ghosh, T.Q. Lian: J. Phys. Chem. B (2001), 105: 4545.
84. S.P. Church, F.W. Grevels, H. Hermann, K. Schaffner: Inorg. Chem. (1985), 24: 418.
85. P.M. Hodges, S.A. Jackson, J. Jacke, M. Poliakoff, J.J. Turner, F.W. Grevels: J. Am. Chem. Soc. (1990), 112: 1234.
86. S.P. Church, F.W. Grevels, H. Hermann, J.M. Kelly, W.E. Klotzbucher, K. Schaffner: J. Chem. Soc., Chem. Commun. (1985), 594.
87. S.P. Church, F.W. Grevels, G.Y. Kiel, W.A. Kiel, J. Takats, K. Schaffner: Angew. Chem., Int. Ed. Engl. (1986), 25: 991.
88. F.W. Grevels, W.E. Klotzbücher, F. Seils, K. Schaffner, J. Takats: J. Am. Chem. Soc. (1990), 112: 1995.
89. F.-W. Grevels, W.E. Klotzbücher, J. Schrickel, K. Schaffner: J. Am. Chem. Soc. (1994), 116: 6229.
90. K.T. Kotz, H. Yang, P.T. Snee, C.K. Payne, C.B. Harris: J. Organomet. Chem. (2000), 596: 183.
91. A. Shagal, R.H. Schultz: Organometallics (2002), 21: 5657.
92. R. Krishnan, R.H. Schultz: Organometallics (2001), 20: 3314.
93. P.C. Ford, S. Massick: Coord. Chem. Rev. (2002), 226: 39.
94. K. Koutsoupakis, S. Stavrakis, E. Pinakoulaki, T. Soulimane, C. Varotsis: J. Biol. Chem. (2002), 277: 32860.
95. S. Stavrakis, K. Koutsoupakis, E. Pinakoulaki, A. Urbani, M. Saraste, C. Varotsis: J. Am. Chem. Soc. (2002), 124: 3814.
96. D. Heitbrink, H. Sigurdson, C. Bolwien, P. Brzezinski, J. Heberle: Biophys. J. (2002), 82: 1.
97. A. Barth, C. Zscherp: Q. Rev. Biophys. (2002), 35: 369.
98. C. Zscherp, A. Barth: Biochemistry (2001), 40: 1875.
99. R. Hienerwadel, D. Thibodeau, F. Lenz, E. Nabedryk, J. Breton, W. Kreutz, W. Mantele: Biochemistry (1992), 31: 5799.
100. J.A. Bailey, F.L. Tomson, S.L. Mecklenburg, G.M. MacDonald, A. Katsonouri, A. Puustinen, R.B. Gennis, W.H. Woodruff, R.B. Dyer: Biochemistry (2002), 41: 2675.
101. S. Franzen, J. Bailey, R.B. Dyer, W.H. Woodruff, R.B. Hu, M.R. Thomas, S.G. Boxer: Biochemistry (2001), 40: 5299.
102. T.P. Causgrove, R.B. Dyer: Biochemistry (1993), 32: 11985.
103. O. Einarsdottir, R.B. Dyer, D.D. Lemon, P.M. Killough, S.M. Hubig, S.J. Atherton, J.J. Lopezgarriga, G. Palmer, W.H. Woodruff: Biochemistry (1993), 32: 12013.
104. R.B. Dyer, K.A. Peterson, P.O. Stoutland, W.H. Woodruff: J. Am. Chem. Soc. (1991), 113: 6276.
105. R.B. Dyer, J.J. Lopezgarriga, O. Einarsdottir, W.H. Woodruff: J. Am. Chem. Soc. (1989), 111: 8962.
106. R.B. Dyer, O. Einarsdottir, P.M. Killough, J.J. Lopezgarriga, W.H. Woodruff: J. Am. Chem. Soc. (1989), 111: 7657.
107. M.T. Zanni, R.M. Hochstrasser: Curr. Opin. Struct. Biol. (2001), 11: 516.
108. R.B. Dyer, F. Gai, W.H. Woodruff: Acc. Chem. Res. (1998), 31: 709.
109. S. Seidel, K. Seppelt: Science (2000), 290: 117.
110. M.A. Graham, R.N. Perutz, M. Poliakoff, J.J. Turner: J. Organomet. Chem. (1972), 34: C34.
111. M. Poliakoff, J.J. Turner: J. Chem. Soc., Dalton Trans. (1974), 2276.
112. R.N. Perutz, J.J. Turner: J. Am. Chem. Soc. (1975), 97: 4791.
113. D.C. Grills, M.W. George: Adv. Inorg. Chem. (2001), 52: 113.
114. M.B. Simpson, M. Poliakoff, J.J. Turner, W.B. Maier II, J.G. McLaughlin: J. Chem. Soc., Chem. Commun. (1983), 1355.
115. J.R. Wells, E. Weitz: J. Am. Chem. Soc. (1992), 114: 2783.
116. M. Jyo-O, H. Takeda, K. Omiya, Y. Ishikawa, S. Arai: Bull. Chem. Soc. Jpn. (1993), 66: 3618.
117. T. Clifford, Fundamentals of Supercritical Fluids, OxfordUniversity Press, Oxford, (1999).
118. C. Hall, R.N. Perutz: Chem. Rev. (1996), 96: 3125.
119. G.I. Childs, C.S. Colley, J. Dyer, D.C. Grills, X.Z. Sun, J. Yang, M.W. George: J. Chem. Soc., Dalton Trans. (2000), 1901.
120. S. Geftakis, G.E. Ball: J. Am. Chem. Soc. (1998), 120: 9953.
121. X.Z. Sun, D.C. Grills, S.M. Nikiforov, M. Poliakoff, M.W. George: J. Am. Chem. Soc. (1997), 119: 7521.
122. A.J. Rest, J.R. Sodeau, D.J. Taylor: J. Chem. Soc., Dalton Trans. (1978), 651.
123. B.S. Creaven, M.W. George, A.G. Ginzburg, C. Hughes, J.M. Kelly, C. Long, I.M. McGrath, M.T. Pryce: Organometallics (1993), 12: 3127.
124. D.C. Grills, G.I. Childs, M.W. George: Chem. Commun. (2000), 1841.
125. D.C. Grills, X.Z. Sun, G.I. Childs, M.W. George: J. Phys. Chem. A (2000), 104: 4300.
126. B.H. Weiller, E.P. Wasserman, R.G. Bergman, C.B. Moore, G.C. Pimentel: J. Am. Chem. Soc. (1989), 111: 8288.
127. R.H. Schultz, A.A. Bengali, M.J. Tauber, B.H. Weiller, E.P. Wasserman, K.R. Kyle, C.B. Moore, R.G. Bergman: J. Am. Chem. Soc. (1994), 116: 7369.
128. A.A. Bengali, R.H. Schultz, C.B. Moore, R.G. Bergman: J. Am. Chem. Soc. (1994), 116: 9585.
129. A.A. Bengali, B.A. Arndtsen, P.M. Burger, R.H. Schultz, B.H. Weiller, K.R. Kyle, C.B. Moore, R.G. Bergman: Pure Appl. Chem. (1995), 67: 281.
130. B.K. McNamara, J.S. Yeston, R.G. Bergman, B.D. Moore: J. Am. Chem. Soc. (1999), 121: 6437.
131. S.E. Bromberg, H. Yang, M.C. Asplund, T. Lian, B.K. McNamara, K.T. Kotz, J.S. Yeston, M. Wilkens, H. Frei, R.G. Bergman, C.B. Harris: Science (1997), 278: 260.
132. M.C. Asplund, P.T. Snee, J.S. Yeston, M.J. Wilkens, C.K. Payne, H. Yang, K.T. Kotz, H. Frei, R.G. Bergman, C.B. Harris: J. Am. Chem. Soc. (2002), 124: 10605.
133. J.B. Asbury, K. Hang, J.S. Yeston, J.G. Cordaro, R.G. Bergman, T. Lian: J. Am. Chem. Soc. (2000), 122: 12870.
134. A.H. Janowicz, R.G. Bergman: J. Am. Chem. Soc. (1982), 104: 352.
135. J.K. Hoyano, W.A.G. Graham: J. Am. Chem. Soc. (1982), 104: 3723.
136. J.M. Buchanan, J.M. Stryker, R.G. Bergman: J. Am. Chem. Soc. (1986), 108: 1537.
137. J.J. Schneider: Angew. Chem., Int. Ed. Engl. (1996), 35: 1068.
138. A.E. Shilov, G.B. Shul’pin: Chem. Rev. (1997), 97: 2879.
139. R.H. Crabtree: J. Chem. Soc., Dalton Trans. (2001), 2437.
140. X.L. Xie, J.D. Simon: J. Am. Chem. Soc. (1990), 112: 1130.
141. G.I. Childs, D.C. Grills, X.Z. Sun, M.W. George: Pure Appl. Chem. (2001), 73: 443.
142. F.P.A. Johnson, M.W. George, V.N. Bagratashvili, L.N. Vereshchagina, M. Poliakoff: Mendeleev Commun. (1991), 26.
143. C.J. Breheny, J.M. Kelly, C. Long, S. O’Keeffe, M.T. Pryce, G. Russell, M.M. Walsh: Organometallics (1998), 17: 3690.
144. Y. Ishikawa, C.E. Brown, P.A. Hackett, D.M. Rayner: Chem. Phys. Lett. (1988), 150: 506.
145. C.E. Brown, Y. Ishikawa, P.A. Hackett, D.M. Rayner: J. Am. Chem. Soc. (1990), 112: 2530.
146. S. Zaric, M.B. Hall: J. Phys. Chem. A (1997), 101: 4646.
147. J.K. Klassen, M. Selke, A.A. Sorensen, G.K. Yang: J. Am. Chem. Soc. (1990), 112: 1267.
148. T.J. Burkey: J. Am. Chem. Soc. (1990), 112: 8329.
149. D.P. Burney and T.J. Burkey, Proceedings of the 207th ACS National Meeting, San Diego, CA, March 13–17, (1994), 207:, 19 - INOR.
150. G.J. Farrell, T.J. Burkey: J. Photochem. Photobiol., A (2000), 137: 135.
151. E.F. Walsh, M.W. George, S. Goff, S.M. Nikiforov, V.K. Popov, X.Z. Sun, M. Poliakoff: J. Phys. Chem. (1996), 100: 19425.
152. T.E. Bitterwolf, K.A. Lott, A.J. Rest, J. Mascetti: J. Organomet. Chem. (1991), 419: 113.