Navegar

Colección

Datos Estadísticas

Artículo

Estamos trabajando para incorporar este artículo al repositorio
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

The electrochemistry of the {RhNO}8 complexes [Rh(PCP tBu)(NO)][BF4] (1+), [Rh(PCP tBuCH2)(NO)][BF4] (2+), and Rh(PCPtBu)(NO)Cl (3) was studied. Both four-coordinate complexes 1+ and 2+ exhibit a reversible reduction within the CH2Cl2 solvent window. Nevertheless, the chemical or electrochemical reduction of 1+ and 2+ in CH 2Cl2 led to the formation of the five-coordinate {RhNO}8 complexes 3 and Rh(PCPtBuCH2)(NO)Cl (4), respectively, through chloride abstraction from CH2Cl 2 by the one-electron-reduced {RhNO}9 species [Rh(PCP tBu)(NO)]• (1•) and [Rh(PCP tBuCH2)(NO)]• (2•), as has been observed for many other 17-electron paramagnetic complexes. The new complex 4 was fully characterized by multinuclear NMR techniques, IR, X-ray diffraction, CV, UV-vis, and elemental analysis. On the other hand, the five-coordinate complexes 3 and 4 show only one irreversible oxidation in CH2Cl2 and two irreversible reductions in THF. The {RhNO}9 complex 1• could be obtained quantitatively by one-electron reduction of 1+ with cobaltocene in nonchlorinated solvents and was characterized by IR, EPR, and 1H NMR in solution. Activation of carbon-halogen bonds by complex 1• was observed by studying the reactivity of 1• with some aryl halides, giving in all cases the {RhNO}8 Rh(PCPtBu)(NO)X (X = Cl -, 3, or X = I-, 6) as the only rhodium complex, while a complex with coordination of the aryl moiety was not observed as a stable final product in any case. The fate of the aryl organic radicals could be determined in some cases. In addition, DFT calculations were performed to elucidate the electronic structure of 1• and to support the observed reactivity. © 2013 American Chemical Society.

Registro:

Documento: Artículo
Título:Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes
Autor:Pellegrino, J.; Gaviglio, C.; Milstein, D.; Doctorovich, F.
Filiación:Departamento de Química Inorgánica, Analítica, y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, C1428EHA, Buenos Aires, Argentina
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Palabras clave:Electrochemical reductions; Electron transfer behavior; Irreversible oxidation; Irreversible reduction; Non-chlorinated solvents; One-electron reductions; Paramagnetic complexes; Spectroscopic characterization; Chlorine; Chlorine compounds; Coordination reactions; Electrolytic reduction; Electronic structure; Iodine; Paramagnetism; Rhodium; X ray diffraction; Rhodium compounds
Año:2013
Volumen:32
Número:21
Página de inicio:6555
Página de fin:6564
DOI: http://dx.doi.org/10.1021/om4008746
Título revista:Organometallics
Título revista abreviado:Organometallics
ISSN:02767333
CODEN:ORGND
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_02767333_v32_n21_p6555_Pellegrino

Referencias:

  • Goodrich, L.E., Paulat, F., Praneeth, V.K.K., Lehnert, N., (2010) Inorg. Chem., 49, pp. 6293-6316
  • Roncaroli, F., Videla, M., Slep, L.D., Olabe, J.A., (2007) Coord. Chem. Rev., 251, pp. 1903-1930
  • Feltham, R.D., Enemark, J.H., (1981) Top. Stereochem., 12, pp. 155-215
  • Enemark, J.H., Feltham, R.D., (1974) Coord. Chem. Rev., 13, pp. 339-406
  • Gunanathan, C., Milstein, D., (2011) Acc. Chem. Res., 44, pp. 588-602
  • Pugh, D., Danopoulos, A.A., (2007) Coord. Chem. Rev., 251, pp. 610-641
  • Szabó, K.J., (2006) Synlett, 6, pp. 811-824
  • Rybtchinski, B., Milstein, D., (2004) ACS Symp. Ser., 885, pp. 70-85
  • Van Der Boom, M.E., Milstein, D., (2003) Chem. Rev., 103, pp. 1759-1792
  • Singleton, J.T., (2003) Tetrahedron, 59, pp. 1837-1857
  • Milstein, D., (2003) Pure Appl. Chem., 75, pp. 445-460
  • Albrecht, M., Van Koten, G., (2001) Angew. Chem., Int. Ed., 40, pp. 3750-3781
  • Vigalok, A., Milstein, D., (2001) Acc. Chem. Res., 34, pp. 798-807
  • Jensen, C.M., (1999) Chem. Commun., pp. 2443-2449
  • Rybtchinski, B., Milstein, D., (1999) Angew. Chem., Int. Ed., 38, pp. 870-883
  • García Serres, R., Grapperhaus, C.A., Bothe, E., Bill, E., Weyhermuller, T., Neese, F., Wieghardt, K., (2004) J. Am. Chem. Soc., 126, pp. 5138-5153
  • Mu, X.H., Kadish, K.M., (1988) Inorg. Chem., 27, pp. 4720-4725
  • Singh, P., Das, A.K., Sarkar, B., Niemeyer, M., Roncaroli, F., Olabe, J.A., Fiedler, J., Kaim, W., (2008) Inorg. Chem., 47, pp. 7106-7113
  • Singh, P., Fiedler, J., Zális, S., Duboc, C., Niemeyer, M., Lissner, F., Schleid, T., Kaim, W., (2007) Inorg Chem., pp. 9254-9261
  • Videla, M., Jacinto, J.S., Baggio, R., Garland, M.T., Singh, P., Kaim, W., Slep, L.D., Olabe, J.A., (2006) Inorg. Chem., 45, pp. 8608-8617
  • Sarkar, S., Sarkar, B., Chanda, N., Kar, S., Mobin, S.M., Fiedler, J., Kaim, W., Lahiri, G.K., (2005) Inorg. Chem., 44, pp. 6092-6099
  • Sellmann, D., Gottschalk-Gaudig, T., Haussinger, D., Heinemann, F.W., Hess, B.A., (2001) Chem. - Eur. J., 7, pp. 2099-2103
  • Singh, P., Sarkar, B., Sieger, M., Niemeyer, M., Fiedler, J., Zális, S., Kaim, W., (2006) Inorg. Chem., 45, pp. 4602-4609
  • Sieger, M., Sarkar, B., Zális, S., Fiedler, J., Escola, N., Doctorovich, F., Olabe, J.A., Kaim, W., (2004) Dalton Trans., pp. 1797-1800
  • Cheng, P.T., Nyburg, S.C., (1975) Inorg. Chem., 14, pp. 327-329
  • Einstein, F.W.B., Sutton, D., Vogel, P.L., (1976) Inorg. Nucl. Chem. Lett., 12, pp. 671-675
  • Gaviglio, C., Ben-David, Y., Shimon, L.J.W., Doctorovich, F., Milstein, D., (2009) Organometallics, 28, pp. 1917-1926
  • Halpern, J., Maher, J.P., (1965) J. Am. Chem. Soc., 87, pp. 5361-5366
  • Chock, P.B., Halpern, J., (1969) J. Am. Chem. Soc., 91, pp. 582-588
  • Kwiatek, J., Seyler, J.K., (1965) J. Organomet. Chem., 3, pp. 421-432
  • Halpern, J., Pribanic, M., (1970) Inorg. Chem., 9, pp. 2616-2618
  • Adamson, A.W., (1956) J. Am. Chem. Soc., 78, pp. 4260-4261
  • Vlcek, A.A., Basolo, F., (1966) Inorg. Chem., 5, pp. 156-158
  • Wrighton, M.S., Ginley, D.S., (1975) J. Am. Chem. Soc., 97, pp. 2065-2072
  • Wrighton, M.S., Ginley, D.S., (1975) J. Am. Chem. Soc., 97, pp. 4246-4251
  • Kuksis, I., Kovács, I., Baird, M.C., (1996) Organometallics, 15, pp. 4991-5002
  • Puschmann, F.F., Grützmacher, H., De Bruin, B., (2010) J. Am. Chem. Soc., 132, pp. 73-75
  • Sofranko, J.A., Eisenberg, R., Kampmeier, J.A., (1980) J. Am. Chem. Soc., 102, pp. 1163-1165
  • Pilloni, G., Zotti, G., Zecchini, S., (1986) J. Organomet. Chem., 317, pp. 357-362
  • Mueller, K.T., Kunin, A.J., Greiner, S., Henderson, T., Kreilick, R.W., Eisenberg, R., (1987) J. Am. Chem. Soc., 109, pp. 6313-6318
  • Kunin, A.J., Nanni, E.J., Eisenberg, R., (1985) Inorg. Chem., 24, pp. 1852-1856
  • Frech, C.M., Ben-David, Y., Weiner, L., Milstein, D., (2006) J. Am. Chem. Soc., 128, pp. 7128-7129
  • Zhu, D., Budzelaar, P.H.M., (2010) Organometallics, 29, pp. 5759-5761
  • Zhu, D., Korobkov, I., Budzelaar, P.H.M., (2012) Organometallics, 31, pp. 3958-3971
  • Di Vaira, M., Ghilardi, C.A., Sacconi, L., (1976) Inorg. Chem., 15, pp. 1555-1561
  • Thyagarajan, S., Incarvito, C.D., Rheingold, A.L., Theopold, K.H., (2003) Inorg. Chim. Acta, 345, pp. 333-339
  • Tomson, N.C., Crimmin, M.R., Petrenko, T., Rosebrugh, L.E., Sproules, S., Boyd, W.C., Bergman, R.G., Wieghardt, K., (2011) J. Am. Chem. Soc., 133, pp. 18785-18801
  • Verat, A.Y., Pink, M., Fan, H., Fullmer, B.C., Telser, J., Caulton, K.G., (2008) Eur. J. Inorg. Chem., 30, pp. 4704-4709
  • Frech, C.M., Shimon, L.J.W., Milstein, D., (2006) Helv. Chim. Acta, 89, pp. 1730-1739
  • Connelly, N.G., Geiger, W.E., (1996) Chem. Rev., 96, pp. 877-910
  • Bultitude, J., Larkworthy, L.F., Mason, J., Povey, D.C., Sandell, B., (1984) Inorg. Chem., 23, pp. 3629-3633
  • Vigalok, A., Milstein, D., (2000) Organometallics, 19, pp. 2061-2064
  • Richter-Addo, G.B., Wheeler, R.A., Hixson, C.A., Chen, L., Khan, M.A., Ellison, M.K., Schulz, C.E., Scheidt, R., (2001) J. Am. Chem. Soc., 123, pp. 6314-6326
  • Wei, Z., Ryan, M.D., (2010) Inorg. Chem., 49, pp. 6948-6954
  • Pellegrino, J., Hübner, R., Doctorovich, F., Kaim, W., (2011) Chem. - Eur. J., 17, pp. 7868-7874
  • Curran, D.P., Keller, A.I., (2006) J. Am. Chem. Soc., 128, pp. 13706-13707
  • Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery Jr., J.A., Pople, J.A., (2004) Gaussian 03, , Revision C.02; Gaussian, Inc. Wallingford, CT
  • Connelly, N.G., Draggett, P.T., Green, M., Kuc, T.A., (1977) J. Chem. Soc., Dalton Trans., pp. 70-73

Citas:

---------- APA ----------
Pellegrino, J., Gaviglio, C., Milstein, D. & Doctorovich, F. (2013) . Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes. Organometallics, 32(21), 6555-6564.
http://dx.doi.org/10.1021/om4008746
---------- CHICAGO ----------
Pellegrino, J., Gaviglio, C., Milstein, D., Doctorovich, F. "Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes" . Organometallics 32, no. 21 (2013) : 6555-6564.
http://dx.doi.org/10.1021/om4008746
---------- MLA ----------
Pellegrino, J., Gaviglio, C., Milstein, D., Doctorovich, F. "Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes" . Organometallics, vol. 32, no. 21, 2013, pp. 6555-6564.
http://dx.doi.org/10.1021/om4008746
---------- VANCOUVER ----------
Pellegrino, J., Gaviglio, C., Milstein, D., Doctorovich, F. Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes. Organometallics. 2013;32(21):6555-6564.
http://dx.doi.org/10.1021/om4008746