Abstract
Reduction of tetranuclear heterometallic complex Mo2Mg2 was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex [MoVIO2Mg(MeOH)2(OMe)4]2 and a partially reduced MoV complex are in good agreement with experimental data. The reduced MoIII complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. E. Shilov, Izv Akad. Nauk. Ser. Khim., 2003, 12, 2417 [Russ. Chem. Bull., Int. Ed., 2003, 52, 2555].
M. Yu. Antipin, L. P. Didenko, L. M. Kachapina, A. E. Shilov, A. K. Shilova, Yu. T. Struchkov, J. Chem. Soc., Chem. Commun., 1989, 1467.
T. A. Bazhenova, M. A. Bazhenova, G. N. Petrova, S. A. Mironova, Kinet. Katal., 2002, 43, 219 [Kinet. Catal., 2002, 43, 592].
M. Yu. Antipin, Yu. T. Struchkov, A. E. Shilov, A. K. Shilova, Gazz. Chim. Ital., 1993, 123, 256.
Z. Janas, P. Sobota, M Kasprzak, T. Glowiak, Chem. Commun., 1996, 2727.
Z. Janas, P. Sobota, M. Klimowicz, S. Szafert, K. Szczegot, L. B. Jerzykiewicz, J. Chem. Soc., Dalton Trans., 1997, 3897.
N. P. Luneva, S. A. Mironova, A. E. Shilov, M. Yu. Antipin, Yu. T. Struchkov, Angew. Chem., Int. Ed. Engl., 1993, 32, 1178.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, and J. A. Pople, Gaussian 98, Revision A.7, Gaussian, Inc., Pittsburgh PA, 1998.
J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865.
D. N. Laikov, Chem. Phys. Lett., 1997, 281, 151.
P. Sobota, J. Utko, Z. Janas, S. Szafer, Chem. Commun., 1996, 1923.
L. Albaric, N. Hovnanian, A. Julbe, C. Guizard, A. Alvarez-Larena, J. Piniella, Polyhedron, 1997, 16, 587.
C. Limberg, A. J. Downs, A. J. Blake, S. Parsons, Inorg. Chem. 1996, 35, 4439.
Yu. V. Petrusha, A. F. Shestakov. Khim. Fiz., 2006, 25, 43 [Russ. Chem. Phys., 2006, 25 (Engl. Transl.)]
Author information
Authors and Affiliations
Corresponding author
Additional information
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008.
Rights and permissions
About this article
Cite this article
Savinykh, T.A., Shestakov, A.F. Geometry and electronic structure of a heterometallic cluster Mo2Mg2 in different oxidation states of Mo: a DFT study. Russ Chem Bull 57, 451–460 (2008). https://doi.org/10.1007/s11172-008-0072-1
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11172-008-0072-1