Abstract
A representative of the new class of organophosphorus ligands, viz., o,o"-dimethylene(tri-p-cresyl) bicyclophosphite (BCP), was studied as a promoter of Rh(acac)(CO)2 in hydrogenation and hydroformylation. BCP enhances the activity and stability of the catalyst much more strongly than analogous organophosphorus ligands used previously (triphenylphosphine, triphenyl phosphite, and etriolphosphite). A reason for this behavior of BCP was studied using NMR spectroscopy, quantum-chemical calculations, and molecular simulation. The high sensitivity of the 1H NMR signals of the methylene groups of BCP toward complexation appears due to the high density of the highest occupied and lowest unoccupied MO of protons of the CH2 groups, especially those directed toward the P atom. The 1H and 31P NMR spectra indicate the formation of hydrides of two types (HRh(BCP)3 and HRh(BCP)4) directly upon the addition of BCP in amounts exceeding that corresponding to the BCP/Rh = 2 ratio to a solution of Rh((acac)(CO)2. The most probable source of the hydride ion is the BCP molecule itself, namely, the bridging CH2 groups. The molecular mechanics simulation showed that in the [Rh(BCP)3]+ complexes the aromatic rings of BCP formed two molecular cavities. These cavities can alternatively open and close, thus providing flexible screening of the catalytic site. This explains the unusual behavior of the Rh complexes with BCP in hydrogenation and hydroformylation.
Similar content being viewed by others
References
B. R. James, Homogeneous Hydrogenation, Wiley, New York, 1973.
H. M. Colquhoun, J. Holton, D. J. Thompson, and M. V. Twig, New Pathways for Organic Synthesis. Practical Applications of Transition Metals, Plenum, New York, 1987.
N. S. Imyanitov, Rhodium Express, 1995, 10-11, 1.
J. Grimblot, J. P. Bonnelle, C. Vaccher, A. Mortreux, and F. Petit, J. Mol. Catal., 1980, 9, 357.
C. Vaccher, A. Mortreux, and F. Petit, J. Mol. Catal., 1981, 12, 329.
M. J. H. Russell, Platinum Metals Rev., 1988, 32, 179.
M. Kranenburg, E. M. van der Burgt, P. C. J. Kamer, and P. W. N. van Leeuwen, Organometallics, 1995, 14, 3081.
R. L. Pruett, Adv. Organomet. Chem., 1974, 17, 1.
C. A. Tolman, Chem. Rev., 1977, 77, 313.
M. T. Reetz, Catalysis Today, 1998, 42, 399.
E. E. Nifant´ev, A. T. Teleshev, A. A. Zhdanov, V. K. Bel´skii, D. Veber, and W. D. Habicher, Dokl. Akad. Nauk, 1999, 366, 202 [Dokl. Chem., 1999 (Engl. Transl.)].
D. Weber, W. D. Habicher, E. E. Nifant´ev, A. T. Teleshev, A. A. Zhdanov, and V. K. Belsky, Phosphorus, Sulfur and Silicon, 1999, 149, 143.
N. V. Kolesnichenko, N. A. Markova, A. T. Teleshev, and E. V. Slivinskii, Izv. Akad. Nauk, Ser. Khim., 1999, 702 [Russ. Chem. Bull., 1999, 48, 698 (Engl. Transl.)].
A. T. Teleshev, N. V. Kolesnichenko, N. A. Markova, E. V. Slivinskii, E. M. Demina, V. I. Kurkin, G. A. Korneeva, S. M. Loktev, and E. E. Nifant´ev, Neftekhimiya, 1991, 31, 11 [Petroleum Chemistry, 1991, 31 (Engl. Transl.)].
A. T. Teleshev, N. V. Kolesnichenko, N. A. Markova, G. V. Terekhova, V. I. Kurkin, E. V. Slivinskii, and E. E. Nifant´ev, Neftekhimiya, 1999, 39, 179 [Petroleum Chemistry, 1999, 39 (Engl. Transl.)].
A. S. Berenblyum, L. I. Lakhman, L. K. Ronzhin, and M. L. Khidekel´, Izv. Akad. Nauk SSSR, Ser. Khim., 1973, 483 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1973, 22 (Engl. Transl.)].
A. B. Koudriavtsev, A. T. Teleshev, A. A. Zhdanov, E. E. Nifant´ev, and W. Linert, Monatsh. Chem., 2001, 132, 1001.
A. T. Teleshev, G. M. Grishina, A. A. Borisenko, N. N. Nevskii, and E. E. Nifant´ev, Zh. Obshch. Khim., 1984, 54, 1710 [J. Gen. Chem. USSR, 1984, 54 (Engl. Transl.)].
Yu. B. Kagan, E. V. Slivinskii, V. I. Kurkin, G. A. Korneeva, R. A. Aranovich, I. G. Fal´kov, N. N. Rzhevskaya, and S. M. Loktev, Neftekhimiya, 1985, 25, 233 [Petroleum Chemistry, 1985, 25 (Engl. Transl.)]
T. G. Cherkasova, M. R. Galding, I. S. Podkorytov, and Yu. S. Varshavsky, Rhodium Express, 1993, 2, 23.
G. Henrici-Olivé and S. Olivé, Coordination and Catalysis, VCH, Weinheim, 1977.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kudryavtsev, A.B., Teleshev, A.T., Nifant"ev, E.E. et al. Unusual behavior of o,o"-dimethylene(tri-p-cresyl) bicyclophosphite as a novel organophosphorus ligand in olefin hydrogenation and hydroformylation. Russian Chemical Bulletin 52, 2740–2746 (2003). https://doi.org/10.1023/B:RUCB.0000019894.03431.ba
Issue Date:
DOI: https://doi.org/10.1023/B:RUCB.0000019894.03431.ba