Abstract
The DFT B3LYP method was used to optimize the geometries, calculate the IR spectra, and analyze the electronic structures of carbonyl(carboxylato)(phosphine)rhodium(I) complexes, namely, trans-[Rh(Cl)(CO)(PPh3)2], trans-[Rh(OCOR)(CO)(PPh3)2] (R = H, CH3, and CF3), and trans-[Rh(OCOH)(CO)(PX3)2], and free PX3 molecules (X = H, F, CH3, i-Pr, Cy, and Ph). A linear correlation between v(CO) in the IR spectra of trans-[Rh(OCOH)(CO)(PX3)2] and the HOMO energy of the free PX3 molecule was found for phosphines with nonaromatic substituents X. It was concluded that the electronic state of the CO group is mainly determined by the σ-donor properties of phosphines. The distinctive features of the electronic structure of triphenylphosphine are discussed.
Similar content being viewed by others
References
Roodt, A., Otto, S., and Steyl, G., Coord. Chem. Rev., 2003, vol. 245, nos. 1–2, p. 121.
Otto, S. and Roodt, A., Inorg. Chim. Acta, 2004, vol. 357, no. 1, p. 1.
Kühl, O., Coord. Chem. Rev., 2005, vol. 249, nos. 5–6, p. 693.
Cooney, K.D., Cundari, T.R., Hoffman, N.W., et al., J. Am. Chem. Soc., 2003, vol. 125, no. 14, p. 4318.
Varshavskii, Yu.S., Cherkasova, T.G., Podkorytov, I.S., et al., Koord. Khim., 2005, vol. 31, no. 2, p. 121.
Sizova, O.V., Varshavskii, Yu.S., and Nikol’skii, A.B., Koord. Khim., 2005, vol. 31, no. 12, p. 921.
Gilheany, D.G., Chem. Rev., 1994, vol. 94, no. 5, p. 1339.
Frisch, M.J., Trucks, G.W., Schlegel, H.B., et al., Gaussian, Inc., Pittsburg (PA, USA), 2003.
Schmidt, M.W., Baldridge, K.K., Boatz, J.A., et al., J. Comput. Chem., 1993, vol. 14, no. 11, p. 1347.
Granovsky, A., PC GAMESS. Version 6.4, Moscow: Moscow State Univ., 2004.
Becke, A.D., J. Chem. Phys., 1993, vol. 98, no. 7, p. 5648.
Wadt, W.R. and Hay, P.J., J. Chem. Phys., 1985, vol. 82, no. 1, p. 284.
Hay, P.J. and Wadt, W.R., J. Chem. Phys., 1985, vol. 82, no. 1, p. 299.
Reed, A.E., Curtiss, L.A., and Weinhold, F., Chem. Rev., 1988, vol. 88, no. 6, p. 899.
Mayer, I., Int. J. Quantum Chem., 1986, vol. 29, no. 1, p. 73.
Mayer, I., Int. J. Quantum Chem., 1986, vol. 29, no. 3, p. 477.
Flukiger, P., Luthi, H.P., Portmann, S., and Weber, J., MOLEKEL, 4.3., Manno (Switzerland): Swiss Center for Scientific Computing, 2000–2002.
Marynick, D.S., J. Am. Chem. Soc., 1984, vol. 106, no. 14, p. 4064.
Orpen, A.G. and Connelly, N.G., Organometallics, 1990, vol. 9, no. 4, p. 1206.
Orpen, A.G. and Connelly, N.G., J. Chem. Soc., Chem. Commun., 1985, no. 19, p. 1310.
Tolman, C.A., Chem. Rev., 1977, vol. 77, no. 3, p. 313.
Lichtenberger, D.L. and Jatcko, M.E., Inorg. Chem., 1992, vol. 31, no. 3, p. 451.
Sokol, V.I., Gol’dshleger, N.F., and Porai-Koshits, M.A., Koord. Khim., 1993, vol. 19, no. 1, p. 47.
Grushin, V.V., Kuznetsov, V.F., Bensimon, C., and Alper, H., Organometallics, 1995, vol. 14, no. 8, p. 3927.
Kemp, G., Roodt, A., and Purcell, W., Rhodium Express, 1995, no. 12, p. 21.
Moigno, D., Kiefer, W., Callejas-Gaspar, B., et al., New J. Chem., 2001, vol. 25, no. 11, p. 1389.
Keim, W., Becker, J., and Trzeciak, A.M., J. Organomet. Chem., 1989, vol. 372, no. 3, p. 447.
Yoshida, T., Thorn, D.L., Okano, T., et al., J. Am. Chem. Soc., 1979, vol. 101, no. 15, p. 4212.
Yarbrough, L.W. and Hall, M.B., Inorg. Chem., 1978, vol. 17, no. 8, p. 2269.
Daamen, H., Oskam, A., and Stufkens, D.J., Inorg. Chim. Acta, 1980, vol. 38, no. 1, p. 71.
Author information
Authors and Affiliations
Additional information
Original Russian Text © O. V. Sizova, Yu.S. Varshavskii, L.V. Skripnikov, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 5, pp. 323–332.
Rights and permissions
About this article
Cite this article
Sizova, O.V., Varshavskii, Y.S. & Skripnikov, L.V. Quantum-chemical study of donor-acceptor interactions in rhodium(I) carbonyl carboxylate complexes with phosphine ligands. Russ J Coord Chem 33, 313–322 (2007). https://doi.org/10.1134/S1070328407050016
Received:
Issue Date:
DOI: https://doi.org/10.1134/S1070328407050016