Iranian Journal of Chemistry

Iranian Journal of Chemistry

Theoretical study of cobalt, rhodium and rhodium-cobalt carbonyl cluster catalysts with general formula ConRhm(CO)12: Investigation of geometric structure, isomeric stability, electronic and vibrational properties

Document Type : Original Article

Authors
Alireza Salimi 1
Zahra Nezhadali Baghan 2
1 Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad
2 Department of Chemistry,Faculty of Science, Ferdowsi University of Mashhad
10.22036/cr.2022.347722.1186
Abstract
To investigate the geometric structure and the effect of metal type and number on the structure of cobalt and rhodium tetranuclear carbonyl cluster catalysts, geometric optimization on the tetranuclear metal clusters of cobalt [Co4(CO)12], rhodium [Rh4(CO)12] and various isomeric structures of mixed cobalt/rhodium metal clusters with different cobalt-rhodium ratios including [Co3Rh(CO)12], [Co2Rh2(CO)12] and [CoRh3(CO)12] were performed using density functional theory (DFT) calculations by B3LYP method and LANL2DZ basis set. The results revealed that in the case of mixed cobalt-rhodium compounds containing [Co3Rh(CO)12], [Co2Rh2(CO)12] and [CoRh3(CO)12], the calculated lowest energy is related to the carbonyl cluster isomeric form in which the rhodium atom is located in the apical region. In addition, the electronic properties and vibration spectroscopy of title compounds were investigated, and which results are in good agreement with the experimental data. The Natural Bond Orbitals (NBO) analysis and LUMO and HOMO energy levels are also calculated and discussed below.

Graphical Abstract

Theoretical study of cobalt, rhodium and rhodium-cobalt carbonyl cluster catalysts with general formula ConRhm(CO)12: Investigation of geometric structure, isomeric stability, electronic and vibrational properties
Keywords
Density functional theory (DFT)
Cobalt carbonyl cluster
Rhodium carbonyl cluster
Rhodium-cobalt carbonyl cluster
Tetranuclear carbonyl cluster catalysts

Subjects

  1. [1] F. A. Cotton, G. Wilkinson, C. A. Murillo, M. Bochmann, Adv. Inorg. Chem. (6th ed) John Wiley.

    New York, 1999.

    [2] M. F. Zhou, L. Andrews, C. W. Bauschlicher, Jr. Chem. Rev. 101, 1931 (2001).

    [3] B. K. Burgess, D. J. Lowe, Chem. Rev. 96, 2983 (1996).

    [4] B. E. Smith, Adv. Inorg. Chem. 47, 159 (1999).

     [5] S. Banerjee, G. R. Kumar, P. Mathur, P. Sekar, Chem. Commun. 299, (1997).

    [6] P. Mathur, S. Ghose, M. M. Hossain, C. V. V. Satyanarayana,  S.  Banerjee,  G. R.   Kumar,   P. B.  Hitchcocks, J. F. Nixon, Organometallics, 16, 3815 (1997).

    [7] C. E. Anson, R. E. Benfield, A. W. Bott, B. F. G. Johnson, D. Braga, E. A. Marseglia, J. Chem. Soc. 

    Chem. Commun. 889, (1988).

    [8] S. Aime, M. Botta, R. Gobetto, B. E. Hanson, Inorg. Chem. 28, 1196 (1989).

    [9] S. Onaka, D. F. Shriver, Inorg. Chem. 15, 915 (1976).

    [10] C. H. Wei, L. F. Dahl, J. Am. Chem. Soc.  88, 1821 (1966).

    [11] M. Torrent, M. Sola, G. Frenking, Chem. Rev. 100, 439 (2000).

    [12] F. Fischer, H. Tropsch, Brennst.  Chem. 4, 276 (1923).

    [13] R. Lazzaroni, R. Settambolo, A. Caiazzo, M. A. Bennett, Organometallics, 21, 2454 (2002).

    [14] C. Li, L. Chen, M. Garland, J. Am. Chem. Soc. 129, 13327 (2007).

    [15] S. Inoue, Y. Fukumoto, N. Chatani, J. Org. Chem. 72, 6588 (2007).

    [16] Y. Fukumoto, M. Hagihara, F. Kinashi, N. Chatani, J. Am. Chem. Soc. 133, 10014 (2011).

    [17]  L. Alvila,  T. A. Pakkanen, T. T. Pakkanen, O. Krause, J. Mol. Catal. 75, 333 (1992).

    [18] I. Ojima, R. J. Donovan, N. Clos, Organometallics, 10, 2606 (1991).

    [19] C. Huo, M. Beller, H. Jiao, Comput. Organomet. Chem. 219 (2011).

    [20] S. Niu, M. B. Hall, Chem. Rev. 100, 353 (2000).

    [21] M. Torrent, M. Sola, G. Frenking, Chem. Rev. 100, 439 (2000). 

    [22] S. Onaka, D. F. Shriver, Inorg. Chem. 15, 915 (1976).

    [23] M. A. Cohen, D. R. Kidd, T. L. Brown, J. Am. Chem. Soc. 97, 4408 (1975).

    [24] J. Evans, B. F. G. Johnson, J. Lewis, J. R. Norton, J. Chem. Soc., Chem. Commun. 807 (1973).

    [25] L. J. Farrugia, J. Cluster Sci. 11, 39 (2000).

    [26] K. Q. Chi, Q. S. Li, Y. Xie, R. B. King, H. F. Schaefer III, Theor. Chem. Acc. 130, 393 (2011). 

    [27] S.  Gong, Q. Luo, N. Dou, Q. Chi, B. Peng, Y.  Xie, R. King, H. F. Schaefer III, J. Phys. Chem. A, 119, 1177 (2015).

    [28] J. Cui, X. Zhou, G. Wang, C. Chi, Z. H. Li, M. Zhou, J. Phys. Chem. A, 118, 2719 (2014).

    [29] Y. Xie, R. B. King, H. F. Schaefer III, Spectrochimica Acta Part A, 61, 1693 (2005).

    [30] X. Feng, J. Gu, Y. Xie, R. B. King,  H. F. Schaefer III,  J. Chem. Theor. Comput. 3, 1580 (2007).

    [31] P. Hirva, M. Haukka, M. Jakonen, M. A. Moreno, J. Mol. Model. 14, 171 (2008).

    [32] S. Ghosh, S. E. Kabir, S. Pervin, A. K. Raha, G. M. Golzar Hossain, D. T. Haworth, S. V. Lindeman,

    1. W. Bennett, T. A. Siddiquee, L. Salassa, H. W. Roesky, Dalton Trans. 3510 (2009).

    [33] I. Del Rosal, F. Jolibois, L. Maron, K. Philippot, B. Chaudret, R. Poteau, Dalton Trans. 2142 (2009).

    [34] Y. Zhao, D. G. Truhlar, J. Chem. Phys. 124, 224105 (2006).

    [35] M. Buhl, H. Kabrede, J. Chem. Theor. Comput. 2, 1282 (2006).

    [36] A. D. Becke, J. Chem. Phys. 98, 5648 (1993).

    [37] C. Lee, W. Yang, R. G. Parr, Phys. Rev. B, 37, 785 (1988).

    [38] Y. Xie, R. B. King, H. F. Schaefer, Spectrochim. Acta, Part A. 61, 1693 (2005).

    [39] X. Feng, J. Gu, Y. Xie, R. B. King, H. F. Schaefer, J. Chem. Theor. Comput. 3, 1580 (2007).

    [40] A. D. Allian, Y. Wang, M. Saeys, G. M. Kuramshina, M. Garland, Vib. Spect. 41, 101

    (2006).

    [41] S. Martinengo, P. Chini, V. G. Albano, F. Cariati, J. Organomet. Chem. 59, 379 (1973).

    [42] D. Labroue, R. Poilblanc, Inorg. Chim. Acta, 6, 387 (1972).

    [43] K. A. Bunten, D. H. Farrar, A. J. Poe, Organometallics. 22, 3448 (2003).

    [44] J. R. Anderson, P. S. Elmes, R. F. Howe, D. E. Mainwaring, J. Catal. 50, 508 (1977).

  • Receive Date 21 June 2022
  • Revise Date 31 August 2022
  • Accept Date 03 September 2022