Hydrogen atom transfer rates from Tp-containing metal-hydrides to trityl radicals
Abstract
The H• transfer rate constants for a series of group 6 molybdenum and tungsten pyrazolyl borate complexes are described. The rate constants for these complexes were found to span a range over 1 magnitude. Analysis of the H• transfer rate constants suggests that a combination of steric, electronic, and enthalpic factors are important in these reactions. Further analysis of the components suggests that the generated 17 e– radicals of these complexes are less electrophilic than the more commonly used CpCr(CO)3H complexes. General implications for H• transfer reactions are discussed.
Résumé
Nous décrivons les constantes de vitesse du transfert de H• pour une série de complexes de pyrazolylborate avec des métaux du groupe 6 (le molybdène et le tungstène). Nous avons observé que les constantes de vitesse de ces complexes s’étendaient sur plus d’un ordre de grandeur. Selon l’analyse des constantes de vitesse du transfert de H•, une combinaison de facteurs stériques, électroniques et enthalpiques serait importante dans ces réactions. Une analyse plus approfondie des composants semble indiquer que les radicaux à 17 e– générés à partir de ces complexes sont moins électrophiles que ceux des complexes CpCr(CO)3H, plus communément employés. Nous discutons des implications générales de ces résultats pour les réactions de transfert de H•.
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References
(1)
Eisenberg D. C. and Norton J. R. Isr. J. Chem. 1991, 31, 55.
(2)
Crossley S. W., Obradors C., Martinez R. M., and Shenvi R. A. Chem. Rev. 2016, 116, 8912.
(3)
Gansäuer A., Otte M., Piestert F., and Fan C.-A. Tetrahedron. 2009, 65, 4984.
(4)
Yao C., Dahmen T., Gansauer A., and Norton J. Science. 2019, 364, 764.
(5)
Choi J., Tang L., and Norton J. R. J. Am. Chem. Soc. 2007, 129, 234.
(6)
Tang L., Papish E. T., Abramo G. P., Norton J. R., Baik M. H., Friesner R. A., and Rappe A. J. Am. Chem. Soc. 2003, 125, 10093.
(7)
Estes D. P., Norton J. R., Jockusch S., and Sattler W. J. Am. Chem. Soc. 2012, 134, 15512.
(8)
Hartung J., Pulling M. E., Smith D. M., Yang D. X., and Norton J. R. Tetrahedron. 2008, 64, 11822.
(9)
Kuo J. L., Hartung J., Han A., and Norton J. R. J. Am. Chem. Soc. 2015, 137, 1036.
(10)
Smith D. M., Pulling M. E., and Norton J. R. J. Am. Chem. Soc. 2007, 129, 770.
(11)
Bullock R. M. and Samsel E. G. J. Am. Chem. Soc. 1990, 112, 6886.
(12)
Pappas I. and Chirik P. J. J. Am. Chem. Soc. 2016, 138, 13379.
(13)
La Porte N. T., Moravec D. B., and Hopkins M. D. Proc. Natl. Acad. Sci. USA. 2014, 111, 9745.
(14)
Chambers G. M., Wiedner E. S., and Bullock R. M. Angew. Chem. Int. Ed. 2018, 57, 13523.
(15)
Ryan O. B., Tilset M., and Parker V. D. J. Am. Chem. Soc. 1990, 112, 2618.
(16)
Norton J. R., Spataru T., Camaioni D. M., Lee S.-J., Li G., Choi J., and Franz J. A. Organometallics. 2014, 33, 2496.
(17)
Capps K. B., Bauer A., Kiss G., and Hoff C. D. J. Organomet. Chem. 1999, 586, 23.
(18)
Yao Q., Bakac A., and Espenson J. H. Organometallics. 1993, 12, 2010.
(19)
Tilset M. and Parker V. D. J. Am. Chem. Soc. 1989, 111, 6711.
(20)
Jordan R. F. and Norton J. R. J. Am. Chem. Soc. 1982, 104, 1255.
(21)
Hoobler R. J., Hutton M. A., Dillard M. M., Castellani M. P., Rheingold A. L., Rieger A. L., Rieger P. H., Richards T. C., and Geiger W. E. Organometallics. 1993, 12, 116.
(22)
Skagestad V. and Tilset M. J. Am. Chem. Soc. 1993, 115, 5077.
(23)
Wise C. F., Agarwal R. G., and Mayer J. M. J. Am. Chem. Soc. 2020, 142, 10681.
(24)
Eisenberg D. C., Lawrie C. J. C., Moody A. E., and Norton J. R. J. Am. Chem. Soc. 1991, 113, 4888.
(25)
Trofimenko S. J. Am. Chem. Soc. 1969, 91, 588.
(26)
Curtis M. D., Shiu K. B., Butler W. M., and Huffman J. C. J. Am. Chem. Soc. 1986, 108, 3335.
(27)
Philipp C. C., White P. S., and Templeton J. L. Inorg. Chem. 1992, 31, 3825.
(28)
McLain S. J. J. Am. Chem. Soc. 1988, 110, 643.
(29)
Landrum J. T. and Hoff C. D. J. Organomet. Chem. 1985, 282, 215.
(30)
Woska D. C., Ni Y., and Wayland B. B. Inorg. Chem. 1999, 38, 4135.
(31)
Protasiewicz J. D. and Theopold K. H. J. Am. Chem. Soc. 1993, 115, 5559.
(32)
Gunasekara T., Abramo G. P., Hansen A., Neugebauer H., Bursch M., Grimme S., and Norton J. R. J. Am. Chem. Soc. 2019, 141, 1882.
(33)
Colle T. H., Glaspie P. S., and Lewis E. S. J. Org. Chem. 1978, 43, 2722.
(34)
Li G., Han A., Pulling M. E., Estes D. P., and Norton J. R. J. Am. Chem. Soc. 2012, 134, 14662.
(35)
Lankamp H., Nauta W. T., and MacLean C. Tetrahedron Lett. 1968, 9, 249.
(36)
Arnett E. M., Flowers R. A., Ludwig R. T., Meekhof A. E., and Walek S. A. J. Phys. Org. Chem. 1997, 10, 499.
(37)
Falivene L., Cao Z., Petta A., Serra L., Poater A., Oliva R., Scarano V., and Cavallo L. Nat. Chem. 2019, 11, 872.
(38)
Roberts B. P. Chem. Soc. Rev. 1999, 28, 25.
(39)
Domingo L. R. and Perez P. Org. Biomol. Chem. 2013, 11, 4350.
(40)
Goerigk L. and Grimme S. J. Chem. Theory Comput. 2011, 7, 291.
(41)
Grimme S., Antony J., Ehrlich S., and Krieg H. J. Chem. Phys. 2010, 132, 154104.
(42)
Grimme S., Ehrlich S., and Goerigk L. J. Comput. Chem. 2011, 32, 1456.
(43)
Axilrod B. M. and Teller E. J. Chem. Phys. 1943, 11, 299.
(44)
Muto Y. Proc. Phys. Soc. Jpn. 1944, 17, 629.
(45)
Zheng J., Xu X., and Truhlar D. G. Theor. Chem. Acc. 2011, 128, 295.
(46)
Brandenburg J. G., Bannwarth C., Hansen A., and Grimme S. J. Chem. Phys. 2018, 148, 064104.
(47)
Caldeweyher E., Bannwarth C., and Grimme S. J. Chem. Phys. 2017, 147, 034112.
(48)
Caldeweyher E., Ehlert S., Hansen A., Neugebauer H., Spicher S., Bannwarth C., and Grimme S. J. Chem. Phys. 2019, 150, 154122.
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Published In
Canadian Journal of Chemistry
Volume 99 • Number 2 • February 2021
Pages: 216 - 220
History
Received: 14 September 2020
Accepted: 9 October 2020
Accepted manuscript online: 20 October 2020
Version of record online: 20 October 2020
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© 2021.
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Hunter B. Vibbert, Hagen Neugebauer, Jack R. Norton, Andreas Hansen, Markus Bursch, and Stefan Grimme. 2021. Hydrogen atom transfer rates from Tp-containing metal-hydrides to trityl radicals. Canadian Journal of Chemistry.
99(2): 216-220. https://doi.org/10.1139/cjc-2020-0392
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