Kinetic Destabilization of Metal–Metal Single Bonds: Isolation of a Pentacoordinate Manganese(0) Monoradical
Douglas W. Agnew
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92193 (USA)
Search for more papers by this authorDr. Curtis E. Moore
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92193 (USA)
Search for more papers by this authorProf. Arnold L. Rheingold
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92193 (USA)
Search for more papers by this authorCorresponding Author
Prof. Joshua S. Figueroa
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92193 (USA)
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92193 (USA)Search for more papers by this authorDouglas W. Agnew
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92193 (USA)
Search for more papers by this authorDr. Curtis E. Moore
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92193 (USA)
Search for more papers by this authorProf. Arnold L. Rheingold
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92193 (USA)
Search for more papers by this authorCorresponding Author
Prof. Joshua S. Figueroa
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92193 (USA)
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92193 (USA)Search for more papers by this authorAbstract
The 17e− monoradical [Mn(CO)5] is widely recognized as an unstable organometallic transient and is known to dimerize rapidly with the formation of a MnMn single bond. As a result of this instability, isolable analogues of [Mn(CO)5] have remained elusive. Herein, we show that two sterically encumbering isocyanide ligands can destabilize the MnMn bond leading to the formation of the isolable, manganese(0) monoradical [Mn(CO)3(CNArDipp2)2] (ArDipp2=2,6-(2,6-(iPr)2C6H3)2C6H3). The persistence of [Mn(CO)3(CNArDipp2)2] has allowed for new insights into nitrosoarene spin-trapping studies of [Mn(CO)5].
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References
- 1M. C. Baird, J. Organomet. Chem. 2014, 751, 50.
- 2C. D. Hoff, Coord. Chem. Rev. 2000, 206–207, 451.
- 3M. C. Baird, Chem. Rev. 1988, 88, 1217.
- 4D. C. Eisenberg, J. R. Norton, Isr. J. Chem. 1991, 31, 55.
- 5R. L. Sweany, J. Halpern, J. Am. Chem. Soc. 1977, 99, 8335.
- 6M. Wrighton, Chem. Rev. 1974, 74, 401.
- 7S. A. Fairhurst, J. R. Morton, R. N. Perutz, K. F. Preston, Organometallics 1984, 3, 1389.
- 8M. C. R. Symons, R. L. Sweany, Organometallics 1982, 1, 834.
- 9J. A. Howard, J. R. Morton, K. F. Preston, Chem. Phys. Lett. 1981, 83, 226.
- 10S. P. Church, M. Poliakoff, J. A. Timney, J. J. Turner, J. Am. Chem. Soc. 1981, 103, 7515.
- 11W. L. Waltz, O. Hackelberg, L. M. Dorfman, A. Wojcicki, J. Am. Chem. Soc. 1978, 100, 7259.
- 12A. Hudson, M. F. Lappert, P. W. Lednor, B. K. Nicholson, J. Chem. Soc. Chem. Commun. 1974, 966.
- 13A. S. Huffadine, B. M. Peake, B. H. Robinson, J. Simpson, P. A. Dawson, J. Organomet. Chem. 1976, 121, 391.
- 14A. Hudson, M. F. Lappert, B. K. Nicholson, J. Chem. Soc. Dalton Trans. 1977, 551.
- 15D. R. Kidd, C. P. Cheng, T. L. Brown, J. Am. Chem. Soc. 1978, 100, 4103.
- 16S. B. McCullen, T. L. Brown, J. Am. Chem. Soc. 1982, 104, 7496.
- 17D. J. Kuchynka, C. Amatore, J. K. Kochi, J. Organomet. Chem. 1987, 328, 133.
- 18G. B. Rattinger, R. L. Belford, H. Walker, T. L. Brown, Inorg. Chem. 1989, 28, 1059.
- 19F. Bourrez, F. Molton, S. Chardon-Noblat, A. Deronzier, Angew. Chem. Int. Ed. 2011, 50, 9903; Angew. Chem. 2011, 123, 10077.
- 20J. M. Smieja, M. D. Sampson, K. A. Grice, E. E. Benson, J. D. Froehlich, C. P. Kubiak, Inorg. Chem. 2013, 52, 2484.
- 21M. D. Sampson, A. D. Nguyen, K. A. Grice, A. L. Rheingold, C. P. Kubiak, J. Am. Chem. Soc. 2014, 136, 5460.
- 22A. E. Carpenter, C. C. Mokhtarzadeh, D. S. Ripatti, I. Havrylyuk, R. Kamezawa, C. E. Moore, A. L. Rheingold, J. S. Figueroa, Inorg. Chem. 2015, 54, 2936.
- 23T. B. Ditri, B. J. Fox, C. E. Moore, A. L. Rheingold, J. S. Figueroa, Inorg. Chem. 2009, 48, 8362.
- 24F. A. Cotton, F. Zingales, J. Am. Chem. Soc. 1961, 83, 351.
- 25M. A. Stewart, C. E. Moore, T. B. Ditri, L. A. Labios, A. L. Rheingold, J. S. Figueroa, Chem. Commun. 2011, 47, 406.
- 26A. W. Addison, T. N. Rao, J. Reedijk, J. van Rijn, G. C. Verschoor, J. Chem. Soc. Dalton Trans. 1984, 1349.
- 27M. Elian, R. Hoffmann, Inorg. Chem. 1975, 14, 1058.
- 28W. J. Shaw, P. Kandandarachchi, J. A. Franz, T. Autrey, Organometallics 2004, 23, 2080.
- 29Likely because of a cis-labilizing effect from the κ1-phosphido unit, 7 is obtained as a mixture of trans:trans and cis:trans (structurally characterized) isomers with respect to the CNArDipp2 ligands. See the text and the Supporting Information.
- 30M. Scheer, G. Balázs, A. Seitz, Chem. Rev. 2010, 110, 4236.
- 31M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev. 2010, 110, 4178.
- 32O. J. Scherer, T. Hilt, G. Wolmershäuser, Organometallics 1998, 17, 4110.
- 33S. Heinl, M. Scheer, Chem. Sci. 2014, 5, 3221.
- 34S. Pelties, D. Herrmann, B. de Bruin, F. Hartl, R. Wolf, Chem. Commun. 2014, 50, 7014.
- 35J. Lee, L. Chen, A. H. West, G. B. Richter-Addo, Chem. Rev. 2002, 102, 1019.
- 36N. C. Tomson, L. A. Labios, T. Weyhermuller, J. S. Figueroa, K. Wieghardt, Inorg. Chem. 2011, 50, 5763.
- 37M. L. H. Green, J. Organomet. Chem. 1995, 500, 127.
- 38L. A. Labios, M. D. Millard, A. L. Rheingold, J. S. Figueroa, J. Am. Chem. Soc. 2009, 131, 11318.
- 39S.-C. Chan, J. England, W.-C. Lee, K. Wieghardt, C.-Y. Wong, ChemPlusChem 2013, 78, 214.
- 40M. S. Askari, B. Girard, M. Murugesu, X. Ottenwaelder, Chem. Commun. 2011, 47, 8055.
- 41T. Iwasa, H. Shimada, A. Takami, H. Matsuzaka, Y. Ishii, M. Hidai, Inorg. Chem. 1999, 38, 2851.
- 42J. D. Atwood, T. L. Brown, J. Am. Chem. Soc. 1975, 97, 3380.
- 43J. A. S. Howell, P. M. Burkinshaw, Chem. Rev. 1983, 83, 557.
- 44R. D. Davy, M. B. Hall, Inorg. Chem. 1989, 28, 3524.
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