A.L. Smith et al. / Polyhedron 29 (2010) 164–169
169
[14] M.P. Hendrich, W. Gunderson, R.K. Behan, M.T. Green, M.P. Mehn, T.A. Betley,
C.C. Lu, J.C. Peters, Proc. Natl. Acad. Sci. USA 103 (2006) 17107.
[15] M.J. Ingleson, M. Pink, H. Fan, K.G. Caulton, J. Am. Chem. Soc. 130 (2008) 4262.
[16] C. Vogel, F.W. Heinemann, J. Sutter, C. Anthon, K. Meyer, Angew. Chem., Int. Ed.
47 (2008) 2681.
[17] J.M. Smith, Comments Inorg. Chem. 29 (2008) 189.
[18] E. Kogut, H.L. Wiencko, L. Zhang, D.E. Cordeau, T.H. Warren, J. Am. Chem. Soc.
127 (2005) 11248.
[19] P.L. Holland, Acc. Chem. Res. 41 (2008) 905.
[20] K.D. Kitiachvili, D.J. Mindiola, G.L. Hillhouse, J. Am. Chem. Soc. 126 (2004)
10554.
[21] G.N. Schrauzer, E. Deutsch, J. Am. Chem. Soc. 91 (1969) 3341.
[22] C.G. Pierpont, C.W. Lange, Prog. Inorg. Chem. 41 (1994) 331.
[23] C.G. Pierpont, Coord. Chem. Rev. 216–217 (2001) 99.
[24] P. Chaudhuri, K. Wieghardt, Prog. Inorg. Chem. 50 (2001) 151.
[25] A.I. Poddel’sky, V.K. Cherkasov, G.A. Abakumov, Coord. Chem. Rev. 253 (2009)
291.
5. Conclusions
The redox-activity of amidophenolate ligands facilitates selec-
tive multielectron reactions at square planar cobalt(III) centers.
The cobalt(III) complexes are not strong outer-sphere reductants.
Instead bond-forming reactions with substrates occur at the metal
center through on-demand, intramolecular delivery of redox
equivalents from ligand-based electron reservoirs. Modulation of
the ligand oxidation state affords a unique mechanism to select
for 2eÀ redox reactivity over potentially competing 1eÀ pathways.
Future studies in this area are focused on exploiting this ligand-
mediated 2eÀ redox capacity for the development of new multi-
electron catalysis cycles for selective bond-making and bond-
breaking transformations of small-molecule organic substrates.
[26] K.M. Kadish, K.M. Smith, R. Guilard (Eds.), The Porphyrin Handbook, Academic
Press, 2000.
[27] K.J. Blackmore, J.W. Ziller, A.F. Heyduk, Inorg. Chem. 44 (2005) 5559.
[28] M.R. Haneline, A.F. Heyduk, J. Am. Chem. Soc. 128 (2006) 8410.
[29] R.A. Zarkesh, J.W. Ziller, A.F. Heyduk, Angew. Chem., Int. Ed. 47 (2008)
4715.
[30] N.A. Ketterer, H. Fan, K.J. Blackmore, X. Yang, J.W. Ziller, M.-H. Baik, A.F.
Heyduk, J. Am. Chem. Soc. 130 (2008) 4364.
[31] K.J. Blackmore, M.B. Sly, M.R. Haneline, J.W. Ziller, A.F. Heyduk, Inorg. Chem. 47
(2008) 10522.
[32] A.I. Nguyen, K.J. Blackmore, S.M. Carter, R.A. Zarkesh, A.F. Heyduk, J. Am. Chem.
Soc. 131 (2009) 3307.
Supplementary data
CCDC 730032 and 730033 contain the supplementary crystallo-
*
graphic data for CoIII(apPh)(isqPh
)
and (Cp 2Co)[CoIII(apiPr)2]Á
2CH3CN. These data can be obtained free of charge via http://
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
[33] S.C. Bart, E. Lobkovsky, E. Bill, P.J. Chirik, J. Am. Chem. Soc. 128 (2006) 5302.
[34] M.W. Bouwkamp, A.C. Bowman, E. Lobkovsky, P.J. Chirik, J. Am. Chem. Soc. 128
(2006) 13340.
Acknowledgements
[35] S.C. Bart, A.C. Bowman, E. Lobkovsky, P.J. Chirik, J. Am. Chem. Soc. 129 (2007)
7212.
[36] C. Stanciu, M.E. Jones, P.E. Fanwick, M.M. Abu-Omar, J. Am. Chem. Soc. 129
(2007) 12400.
[37] C. Mukherjee, T. Weyhermueller, E. Bothe, P. Chaudhuri, Inorg. Chem. 47
(2008) 2740.
[38] C.J. Rolle, K.I. Hardcastle, J.D. Soper, Inorg. Chem. 47 (2008) 1892.
[39] C.C. Lu, T. Weyhermueller, E. Bill, K. Wieghardt, Inorg. Chem. 48 (2009) 6055.
[40] G.A. Abakumov, V.K. Cherkasov, M.P. Bubnov, L.G. Abakumova, V.N. Ikorskii,
G.V. Romanenko, A.I. Poddel’sky, Russ. Chem. Bull. 55 (2006) 44.
[41] A.I. Poddel’sky, V.K. Cherkasov, G.K. Fukin, M.P. Bubnov, L.G. Abakumova, G.A.
Abakumov, Inorg. Chim. Acta 357 (2004) 3632.
We gratefully acknowledge financial support from the ACS
Petroleum Research Fund (45130-G3) and the Georgia Institute
of Technology. We thank Dr. Les Gelbaum for assistance with
NMR spectroscopy, and David Bostwick for assistance with mass
spectrometry.
References
[42] D.F. Evans, J. Chem. Soc. (1959) 2003.
[43] D.H. Live, S.I. Chan, Anal. Chem. 42 (1970) 791.
[44] P. Chaudhuri, C.N. Verani, E. Bill, E. Bothe, T. Weyhermueller, K. Wieghardt, J.
Am. Chem. Soc. 123 (2001) 2213.
[45] G.A. Abakumov, N.O. Druzhkov, Y.A. Kurskii, A.S. Shavyrin, Russ. Chem. Bull. 52
(2003) 712.
[46] E. Bill, E. Bothe, P. Chaudhuri, K. Chlopek, D. Herebian, S. Kokatam, K. Ray, T.
Weyhermueller, F. Neese, K. Wieghardt, Chem. Eur. J. 11 (2005) 204.
[47] APEX II, Analytical X-Ray Systems, Brukers AXS, Inc., Madison, WI, 2005.
[48] SAINT Version 6.45A, Analytical X-ray Systems, Brukers AXS, Inc., Madison, WI,
2003.
[49] SHELXTL Version 6.12, Analytical X-ray Systems, Bruker AXS, Inc., Madison, WI,
2002.
[50] N.G. Connelly, W.E. Geiger, Chem. Rev. 96 (1996) 877.
[51] D. Herebian, P. Ghosh, H. Chun, E. Bothe, T. Weyhermuller, K. Wieghardt, Eur. J.
Inorg. Chem. (2002) 1957.
[1] N.S. Lewis, D.G. Nocera, Proc. Natl. Acad. Sci. USA 103 (2006) 15729.
[2] R. Eisenberg, D.G. Nocera, Inorg. Chem. 44 (2005) 6799.
[3] U.S. Department of Energy, Report of the Basic Energy Sciences Workshop on
Solar Energy Utilization, Washington, D.C., 2005.
[4] U.S. Department of Energy, Report from the Basic Energy Science Workshop
Washington, D.C., 2007.
[5] B.M. Trost, I. Fleming (Eds.), Comprehensive Organic Synthesis: Selectivity,
Strategy and Efficiency in Modern Organic Chemistry, vol. 9 Set, Pergamon
press, 1992.
[6] A. de Meijere, F. Diederich (Eds.), Metal-Catalyzed Cross-Coupling Reactions,
Second Completely Revised and Enlarged Edition, vol. 1, Wiley-VCH, 2004.
[7] J.F. Hartwig, in: Activation and Functionalization of C–H Bonds, vol. 885, 2004,
Oxford University Press, pp. 136.
[8] S.S. Stahl, Angew. Chem., Int. Ed. 43 (2004) 3400.
[9] S.S. Stahl, J.A. Labinger, J.E. Bercaw, Angew. Chem., Int. Ed. 37 (1998) 2181.
[10] K.I. Goldberg, A.S. Goldman (Eds.), Activation and Functionalization of C–H
Bonds, Oxford University Press, 2004.
[52] S. France, H. Wack, A.E. Taggi, A.M. Hafez, T.R. Wagerle, M.H. Shah, C.L. Dusich,
T. Lectka, J. Am. Chem. Soc. 126 (2004) 4245.
[53] D.G. Brown, Prog. Inorg. Chem. 18 (1973) 177.
[54] Y. Hisaeda, T. Nishioka, Y. Inoue, K. Asada, T. Hayashi, Coord. Chem. Rev. 198
(2000) 21.
[11] J.A. Labinger, J.E. Bercaw, Nature 417 (2002) 507.
[12] N.N. Greenwood, A. Earnshaw, Chemistry of the Elements, second ed.,
Butterworth Heinemann 1997.
[55] X.L. Hu, B.S. Brunschwig, J.C. Peters, J. Am. Chem. Soc. 129 (2007) 8988.
[13] A.B.P. Lever, Comprehensive Coordination Chemistry II, Elsevier Science 2004.