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Abstract:

The new linear homotrinuclear compound frans-[CIRuII(py) 4(NC)RuII(py)4(CN)RuII(py) 4(NO)](PF6)4 was prepared by reaction between the nitro complex trans-[(NC)RuII(py)4(CN)Ru II(py)4(NO2)]+ and the solvento complex obtained by reaction between [CIRuII(py)4(NO)] 3+ and N3- in acetone. The trans-[CIRu II(py)4 (NC)RuII(py)4(CN)Ru II(py)4(NO)]4+ ion (I) has been characterized by 1H NMR and IR spectroscopy (vN0 = 1919 cm -1). This species displays intense electronic absorptions in the visible region which can be assigned to donor-acceptor charge-transfer transitions (DACT) involving {RuNO}6-centered acceptor orbitals and donor orbitals located on the two different neighboring metal centers at ca. 6.7 and 12.6 Å distance from the metal in the {RuNO}6 fragment. Addition of OH- to I generated the nitro complex with a second-order rate constant of (12.5 ± 0.2) × 103 M-1 s-1 (25 ̊C). Cyclic oltammetry experiments complemented by spectroelectrochemistry in the UV-vis-NIR region reveal that I can be reversibly reduced at 0.49 or 0.20 V vs AgCI/Ag for acetonitrile and water, respectively, and oxidized at 0.71 or 0.57 V vs AgCI/Ag. The spectroscopic and spectroelectrochemical information (UV-vis-NIR, X-band EPR) supplemented with electronic structure computation (DFT) reveals that the one-electron reduction is centered on the nitrosyl moiety to yield a {RuNO}7 species, while oxidation occurs on the chlororuthenium side of the molecule. Both processes yield significant changes of the electronic spectra which are discussed in parallel with the electronic structure picture as obtained by DFT. © 2009 American Chemical Society.

Registro:

Documento: Artículo
Título:AII-frans-[CIRuII(py)4(NC)RuII(py) 4(CN)RuII(py)4(N0)](PF6) 4: a redox-active 2-donor/1-acceptor system based on the electrophilic {RuNO}6 motif
Autor:De Candia, A.G.; Singh, P.; Kaim, W.; Slep, L.D.
Filiación:Departamento de Química Inorgánica, Analítica y Química Física, INQUIMAE, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina
Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany
Año:2009
Volumen:48
Número:2
Página de inicio:565
Página de fin:573
DOI: http://dx.doi.org/10.1021/ic801347d
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v48_n2_p565_DeCandia

Referencias:

  • Mallah, T.; Thi6baut, S.; Verdaguer, M.; Veillet, P. Science 1993, 1554; Bignozzi, C.A., Chiorboli, C., Indelli, M.T., Scandola, F., Bertolasi, V., Gilli, G., (1994) J. Chem. Soc, Dalton Trans, pp. 2391-2395
  • Entley, W.R., Girolami, G.S., (1995) Science, 268, pp. 397-100
  • Balzani, V.; Juris, A.; Venturi, M.; Campagna, S.; S. Serroni, S. Chem. Rev. 1996, 759; Bignozzi, C.A., Argazzi, R., Bortolini, O., Scandola, F., Haniman, A., (1996) New J. Chem, 20, pp. 731-738
  • Bignozzi, C.A., Schoonover, J.R., Scandola, F., (1997) Prog. Jnorg. Chem, p. 1
  • Heintz, K.R.D.A.R.A., (1997) Prog. Inorg. Chem, p. 283
  • Vahrenkamp, H., Geiss, A., Richardson, G.N., (1997) J. Chem. Soc, Dalton Trans, pp. 3643-3651
  • Balzani, V., Campagna, S., Denti, G., Juris, A., Serroni, S., Venturi, M., (1998) Acc. Chem. Res, p. 26
  • Richardson, G.N., Brand, U., Vahrenkamp, H., (1999) Inorg. Chem, 38, pp. 3070-3079
  • Zhu, N.Y., Vahrenkamp, H., (1999) J. Organomet. Chem, 573, pp. 67-72
  • Chen, Z.N., Appelt, R., Vahrenkamp, H., (2000) Inorg. Chim. Acta, 309, pp. 65-71
  • Geiss, A., Vahrenkamp, H., (2000) Inorg. Chem, 39, pp. 4029-4036
  • Richardson, G.N., Vahrenkamp, H., (2000) J. Organomet. Chem, 594, pp. 44-48
  • Launay, J.P., Coudret, C., Wires based on metal complexes (2001) Electron Transfer in Chemistry, 5. , Balzani, V, Ed, Wiley-VCH: Weinheim
  • Appelt, R., Vahrenkamp, H., (2003) Z. Anorg. Allg. Chem, 629, pp. 133-138
  • Albores, P., Slep, L.D., Weyhermuller, T., Baraldo, L.M., (2004) Inorg. Chem, 43, pp. 6762-6773
  • Sheng, T.L., Vahrenkamp, H., (2004) Eur. J. Inorg. Chem, 119, pp. 8-1203
  • Vahrenkamp, H., Sheng, T., (2004) Inorg. Chim. Acta, 357, p. 1739
  • Albores, P., Rossi, M.B., Baraldo, L.M., Slep, L.D., (2006) Inorg. Chem, 45, pp. 10595-10604
  • Richter-Addo, G.B., Legzdins, P., (1992) Metal Nitrosyls, , Oxford University Press: New York
  • Olabe, J.A., Slep, L.D., Reactivity and Structure of Complexes of Small Molecules: Nitric and Nitrous Oxide (2004) Comprehensive Coordination Chemistry II, from Biology to Nanotechnology, 1, pp. 603-623. , Mc Cleverty, J. A, Meyer, T. J, Eds, Elsevier: Oxford
  • Enemark, J.H., Feltham, R.D., (1974) Coord. Chem. Rev, 13, pp. 339-406
  • Feltham, R.D., Enemark, J.H., (1981) Top. Stereochem, p. 155
  • Westcott, B.L., Enemark, J.H., (1999) Transition Metal Nitrosyls. In Inorganic Electronic Structure and Spectroscopy, 2, pp. 403-450. , Solomon, E. I, Lever, A. B. P, Eds, John Wiley & Sons: New York
  • Bottomley, F., (1989) Reactions of Coordinated Ligands, 2. , Braterman, P. S, Ed, Plenum: New York
  • Roncaroli, F., Baraldo, L.M., Slep, L.D., Olabe, J.A., (2002) Inorg. Chem, 41, pp. 1930-1939
  • Coe, B.J., Meyer, T.J., White, P.S., (1995) Inorg. Chem, 34, pp. 3600-3609
  • Coe, B.J., Meyer, T.J., White, P.S., (1995) Inorg. Chem, 34, pp. 593-602
  • Bottomley, F., Mukaida, M., (1982) J. Chem. Soc, Dalton Trans, pp. 1933-1937
  • Alessio, E., Mestroni, G., Nardin, G., Attia, W.M., Calligaris, M., Sava, G., Zorzet, S., (1988) Inorg. Chem, 27, pp. 4099-4106
  • Armarego, W.L.F., Perrin, D.D., (1996) Purification of Laboratory Chemicals, , Reed Educational & Professional Publishing Ltd, Oxford
  • Kaim, W., Ernst, S., Kasack, V., (1990) J. Am. Chem. Soc, 112, p. 173
  • Noviandri, I., Brown, K.N., Fleming, D.S., Gulyas, P.T., Lay, P.A., Masters, A.F., Phillips, L., (1999) J. Phys. Chem. B, 103, pp. 6713-6722
  • Malinovsky, E.R., (1991) Factor Analysis in Chemistry, , 2nd ed, Wiley-Interscience: New York
  • Parise, A.R., Pollak, S., Slep, L.D., Olabe, J.A., (1995) An. Asoc. Quim. Argent, 83, pp. 211-223
  • Slep, L.D., Mijovilovich, A., Meyer-Klaucke, W., Weyhermuller, T., Bill, E., Bothe, E., Neese, F., Wieghardt, K., (2003) J. Am. Chem. Soc, 125, pp. 15554-15570
  • Frisch, M.J., (2004) Gaussian 03, Rev. C.02 and D.01, , Gaussian, Inc, Wallingford, CT
  • Szabo, A.; Ostlund, N. S. Modern Quantum Chemistry. Introduction Advanced Electronic Structure Theory, 1st ed.; Dover Publications, Inc.: Mineola, NY, 1989; Olabe, J.A., (2004) Adv. Inorg. Chem, 55, pp. 61-126
  • Callahan, R.W., Meyer, T.J., (1977) Inorg. Chem, 16, pp. 574-581
  • 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
  • Mondal, B., Paul, H., Puranik, V.G., Lahiri, G.K., (2001) J. Chem. Soc., Dalton Trans, pp. 481-487
  • Chanda, N., Paul, D., Kar, S., Mobin, S.M., Datta, A., Puranik, V.G., Rao, K.K., Lahiri, G.K., (2005) Inorg. Chem, 44, pp. 3499-3511
  • Chanda, N., Mobin, S.M., Puranik, V.G., Datta, A., Niemeyer, M., Lahiri, G.K., (2004) Inorg. Chem, 43, pp. 1056-1064
  • Wanat, A., Schneppensieper, T., Stochel, G., van Eldik, R., Bill, E., Wieghardt, K., (2002) Inorg. Chem, 41, pp. 4-10
  • Westre, T.E., Di Cicco, A., Filipponi, A., Natoli, C.R., Hedman, B., Solomon, E.I., Hodgson, K.O., (1994) J. Am. Chem. Soc, 116, pp. 6757-6768
  • Brown, C.A., Pavlosky, M.A., Westre, T.E., Zhang, Y., Hedman, B., Hodgson, K.O., Solomon, E.I., (1992) J. Am. Chem. Soc, 114, pp. 9189-9191
  • Sellmann, D., Blum, N., Heinemann, F.W., Hess, B.A., (2001) Chem. Eur. J, 7, pp. 1874-1879
  • McGarvey, B.R., Ferro, A.A., Tfouni, E., Bezerra, C.W.B., Bagatin, I., Franco, D.W., (2000) Inorg. Chem, 39, pp. 3577-3581
  • Serres, R.G., Grapperhaus, C.A., Bothe, E., Bill, E., Weyhermuller, T., Neese, F., Wieghardt, K., (2004) J. Am. Chem. Soc, 126, pp. 5138-5153
  • Li, M., Bonnet, D., Bill, E., Neese, F., Weyhermuller, T., Blum, N., Sellmann, D., Wieghardt, K., (2002) Inorg. Chem, 41, pp. 3444-3456
  • Wanner, M., Scheiring, T., Kaim, W., Slep, L.D., Baraldo, L.M., Olabe, J.A., Zalis, S., Baerends, E.J., (2001) Inorg. Chem, 40, pp. 5704-5707
  • Frantz, S., Sarkar, B., Sieger, M., Kaim, W., Roncaroli, F., Olabe, J.A., Zalis, S., (2004) Eur. J. Inorg. Chem, 290, pp. 2-2907
  • Roncaroli, F., Ruggiero, M.E., Franco, D.W., Estiu, G.L., Olabe, J.A., (2002) Inorg. Chem, 41, pp. 5760-5769
  • Li, J., Noodleman, L., Case, D.A., Electronic Structure Calculations: Density Functional Methods with Applications to Transition Metal Complexes (1999) Inorganic Electronic Structure and Spectroscopy, J, p. 661. , Solomon, E. I, Lever, A. B. P, Eds, John Wiley & Sons: New York
  • 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
  • Fuoss, R.M., (1958) J. Am. Chem. Soc, 80, pp. 5059-5061
  • The maxima reported here arise from a Gaussian deconvolution performed over the experimental absorption profile in order to obtain the area of the overlapping bands. For this reason the numbers differ slightly form those reported in Table 1; von Kameke, A., Tom, G.M., Taube, H., (1978) Inorg. Chem, 17, pp. 1790-1796
  • Macatangay, A.V., Endicott, J.F., (2000) Inorg. Chem, 39, pp. 437-446
  • Robin, M.B., Day, P., (1967) Adv. Inorg. Chem. Radiochem, 10, p. 247

Citas:

---------- APA ----------
De Candia, A.G., Singh, P., Kaim, W. & Slep, L.D. (2009) . AII-frans-[CIRuII(py)4(NC)RuII(py) 4(CN)RuII(py)4(N0)](PF6) 4: a redox-active 2-donor/1-acceptor system based on the electrophilic {RuNO}6 motif. Inorganic Chemistry, 48(2), 565-573.
http://dx.doi.org/10.1021/ic801347d
---------- CHICAGO ----------
De Candia, A.G., Singh, P., Kaim, W., Slep, L.D. "AII-frans-[CIRuII(py)4(NC)RuII(py) 4(CN)RuII(py)4(N0)](PF6) 4: a redox-active 2-donor/1-acceptor system based on the electrophilic {RuNO}6 motif" . Inorganic Chemistry 48, no. 2 (2009) : 565-573.
http://dx.doi.org/10.1021/ic801347d
---------- MLA ----------
De Candia, A.G., Singh, P., Kaim, W., Slep, L.D. "AII-frans-[CIRuII(py)4(NC)RuII(py) 4(CN)RuII(py)4(N0)](PF6) 4: a redox-active 2-donor/1-acceptor system based on the electrophilic {RuNO}6 motif" . Inorganic Chemistry, vol. 48, no. 2, 2009, pp. 565-573.
http://dx.doi.org/10.1021/ic801347d
---------- VANCOUVER ----------
De Candia, A.G., Singh, P., Kaim, W., Slep, L.D. AII-frans-[CIRuII(py)4(NC)RuII(py) 4(CN)RuII(py)4(N0)](PF6) 4: a redox-active 2-donor/1-acceptor system based on the electrophilic {RuNO}6 motif. Inorg. Chem. 2009;48(2):565-573.
http://dx.doi.org/10.1021/ic801347d