JOURNAL OF CHILEAN CHEMICAL SOCIETY

Vol 67 No 1 (2022): Journal of the Chilean Chemical Society
Original Research Papers

AN IMPROVED SYNTHESIS OF P-PHENYLENE-BRIDGED METHYLATED BINUCLEAR FERROCENE

PDF
  • Yavaraja Dibdalli,
  • Cristian Valdebenito,
  • Mungalimane K. Amshumali,
  • Elies Molins,
  • Cesar Morales-Verdejo
Yavaraja Dibdalli
Department of Chemistry/Industrial Chemistry, Vijayanagara Sri Krishnadevaraya University, Vinayakanagara, Cantonment, Ballari, 583105, Karnataka, India.
Cristian Valdebenito
Universidad Bernardo OHiggins, Facultad de Ciencias de la Salud, Centro Integrativo de Biología y Química Aplicada (CIBQA), General Gana 1702, Santiago, Chile.
Mungalimane K. Amshumali
Department of Chemistry/Industrial Chemistry, Vijayanagara Sri Krishnadevaraya University, Vinayakanagara, Cantonment, Ballari, 583105, Karnataka, India
Elies Molins
3 Institut de Ciencia de Materials de Barcelona (CSIC), Campus UAB, 08193 Bellaterra, Spain
Cesar Morales-Verdejo
Universidad Bernardo OHiggins, Facultad de Ciencias de la Salud, Centro Integrativo de Biología y Química Aplicada (CIBQA), General Gana 1702, Santiago, Chile.
Published February 21, 2022
Keywords
  • Ferrocene,
  • Mössbauer Spectroscopy,
  • mixed-valence
How to Cite
Dibdalli, Y., Valdebenito, C., Amshumali, M., Molins, E., & Morales, C. (2022). AN IMPROVED SYNTHESIS OF P-PHENYLENE-BRIDGED METHYLATED BINUCLEAR FERROCENE. Journal of the Chilean Chemical Society, 67(1), 5414-5417. Retrieved from https://jcchems.com/index.php/JCCHEMS/article/view/1810

Copyright (c) 2022 SChQ

Creative Commons License

This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.

Abstract

This contribution describes an updated synthetic route along with full characterization of [{CpFe}2-p-Ph’] with p-Ph’: p-Bis{2,3,4,5-tetramethylcyclopentadienyl}benzene). The complex reported here was characterized by 1H and 13C NMR, elemental analysis, the X-ray crystal structure, and Mössbauer spectroscopy. From the crystallographic analysis, it was found that both {CpFe} fragments are coordinated to opposite sites of the p-Ph’ ligand. In addition, the analysis through of 1H and 13C NMR spectroscopy, confirm that the synthesis and yield of just one isomer of this compound.

 

1810.JPG

PDF

References

  1. References
  2. P. Aguirre-Etcheverry, D. O’Hare, Electronic communication through unsaturated hydrocarbon bridges in homobimetallic organometallic complexes, Chem. Rev. 110 (2010) 4839–4864. doi:10.1021/cr9003852.
  3. E.E. Bunel, L. Valle, N.L. Jones, P.J. Carroll, C. Barra, M. Gonzalez, N. Munoz, G. Visconti, A. Aizman, J.M. Manriquez, Bis[(pentamethylcyclopentadienyl)metal]pentalenes. A new class of highly delocalized, fused metallocenes, J. Am. Chem. Soc. 110 (1988) 6596–6598. doi:10.1021/ja00227a068.
  4. B. Oelckers, I. Chavez, J.M. Manriquez, E. Roman, On the way to delocalized organometallic polymers: triple- and quadruple-decker pentalene complexes of iron and cobalt, Organometallics. 12 (1993) 3396–3397.
  5. A. Muñoz-Castro, D. Mac-Leod Carey, C. Morales-Verdejo, I. Chávez, J.M. Manríquez, R. Arratia-Pérez, Toward the synthetic control of the HOMO-LUMO gap in binuclear systems: insights from density functional calculations., Inorg. Chem. 49 (2010) 4175–8. doi:10.1021/ic902326y.
  6. M.T. Garland, S. Kahlal, D.M.-L. Carey, R. Arratia-Pérez, J.M. Manríquez, J.-Y. Saillard, Electronic structure and metal–metal communication in (CpM)2(as-indacene) and (CpM)2(s-indacene) (M = Mn, Fe, Co, Ni) complexes: a DFT investigation, New J. Chem. 35 (2011) 2136. doi:10.1039/c1nj20240e.
  7. D. Mac-Leod Carey, C. Morales-Verdejo, a. Muñoz-Castro, F. Burgos, D. Abril, C. Adams, E. Molins, O. Cador, I. Chávez, J.M. Manríquez, R. Arratia-Pérez, J.Y. Saillard, [Cp*Ru(s-indacene)RuCp*] and [Cp*Ru(s-indacene)RuCp*]+: Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems, Polyhedron. 29 (2010) 1137–1143. doi:10.1016/j.poly.2009.12.002.
  8. H. Sano, Mixed-valence states of iron in binuclear ferrocene compounds, Hyperfine Interact. 53 (1990) 97–112. doi:10.1007/BF02101042.
  9. C. Li, H. Yang, J. Xie, K. Wang, J. Li, Q. Zhang, Ferrocene-Based Mixed-Valence Metal − Organic Framework as an E ffi cient and Stable Cathode for Lithium-Ion-Based Dual-Ion Battery, ACS Appl. Mater. Interfaces. 12 (2020) 32719−32725. doi:10.1021/acsami.0c07729.
  10. E.E. Bunel, P. Campos, J. Ruz, L. Valle, I. Chadwick, M. Santa Ana, G. Gonzalez, J.M. Manriquez, Syntheses of p-phenylene- and p-biphenylylene-bridged methylated binuclear ferrocenes, Organometallics. 7 (1988) 474–476. doi:10.1021/om00092a037.
  11. J. Rouzaud, A. Castel, P. Rivière, H. Gornitzka, J.M. Manriquez, Synthesis and Characterization of Novel p -Phenylene- and p -Biphenylene-Bridged Germanocenes, Organometallics. 19 (2000) 4678–4680. doi:10.1021/om000457h.
  12. S. Jiingling, R. Miilhaupt, H. Plenio, Cooperative effects in binuclear zirconocenes : as catalyst in propene polymerization, J. Organomet. Chem. 460 (1993) 191–195. doi:10.1016/0022-328X(93)83145-L.
  13. P. Povea, J.L. Arroyo, G. Carreño, Á. Norambuena, P.L. Rios, M.B. Camarada, I. Chavez, J.M. Manriquez, C. Morales-Verdejo, Catalytic effects of p-phenylene-bridged methylated binuclear ferrocenes on thermal decomposition of the main component of composite solid propellants, Thermochim. Acta. 666 (2018) 181–189. doi:10.1016/j.tca.2018.06.020.
  14. J.L. Arroyo, P. Povea, R. Faúndez, M.B. Camarada, C. Cerda-cavieres, G. Abarca, J.M. Manriquez, C. Morales-Verdejo, Influence iron-iron distance on the thermal decomposition of ammonium perchlorate . New catalysts for the highly efficient combustion of solid rocket propellant, J. Organomet. Chem. J. 905 (2020) 121020. doi:10.1016/j.jorganchem.2019.121020.
  15. C.L.L. Chai, W.L.F. Armarego, Purification of Laboratory Chemicals, 5th ed, Oxford, 2003. https://www.sciencedirect.com/book/9780128054574/purification-of-laboratory-chemicals#book-info.
  16. E.E. Bunel, L. Valle, J.M. Manriquez, Pentamethyicyclopentadlenyi Acetylacetonate Complexes of Iron(II), Cobalt(II), and Nickel(II). Convenient Synthetlc Entries to Mono-h5-C5Me5 Derivatives, Organometallics. 4 (1985) 1680–1682. doi:10.1021/om00128a034.
  17. T.K. Panda, M.T. Gamer, P.W. Roesky, An Improved Synthesis of Sodium and Potassium Cyclopentadienide, Organometallics. 22 (2003) 877–878. doi:10.1021/om0207865.
  18. G.M. Sheldrick, Phase annealing in {it SHELX}-90: direct methods for larger structures, Acta Crystallogr. Sect. A. 46 (1990) 467–473. doi:10.1107/S0108767390000277.
  19. L.J. Farrugia, WinGX and ORTEP for Windows: an update, J. Appl. Crystallogr. 45 (2012) 849–854. doi:10.1107/S0021889812029111.
  20. A. Ceccon, A. Bisello, L. Crociani, A. Gambaro, P. Ganis, F. Manoli, S. Santi, A. Venzo, Synthesis, structure and reactivity of homobimetallic Rh(I) and Ir(I) complexes of s- and as-indacene-diide, J. Organomet. Chem. 600 (2000) 94–111. doi:10.1016/S0022-328X(00)00034-6.
  21. J.M. Manriquez, M.D. Ward, W.M. Reiff, J.C. Calabrese, N.L. Jones, P.J. Carroll, E.E. Bunel, J.S. Miller, Structural and Physical Properties of Delocalized Mixed-Valent [Cp*M(pentalene)M’Cp*]n+ and [Cp*M(indacene)M’Cp*]n+ (M, M’ = Fe, Co, Ni; n = 0, 1, 2) Complexes, J. Am. Chem. Soc. 117 (1995) 6182–6193. doi:10.1021/ja00128a004.
  22. F. Paul, C. Lapinte, Organometallic molecular wires and other nanoscale-sized devices: An approach using the organoiron (dppe)Cp*Fe building block, Coord. Chem. Rev. 178 (1998) 431–509. doi:10.1016/S0010-8545(98)00150-7.
  23. W.R. Browne, R. Hage, J.G. Vos, Tuning interaction in dinuclear ruthenium complexes: HOMO versus LUMO mediated superexchange through azole and azine bridges, Coord. Chem. Rev. 250 (2006) 1653–1668. doi:10.1016/j.ccr.2005.12.008.
  24. D. Mac-Leod Carey, C. Morales-Verdejo, A. Muñoz-Castro, F. Burgos, D. Abril, C. Adams, E. Molins, O. Cador, I. Chávez, J.M. Manríquez, R. Arratia-Pérez, J.Y. Saillard, [Cp*Ru(s-indacene)RuCp*] and [Cp*Ru(s-indacene)RuCp*]+: Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems, Polyhedron. 29 (2010). doi:10.1016/j.poly.2009.12.002.
  25. C. Morales-Verdejo, M.B. Camarada, V. Morales, Á. Cañete, I. Martínez, J.M. Manriquez, I. Chávez, Preliminary results of the reaction of cyclotrimerization of phenylacetylene [2+2+2] catalyzed by [(Cp∗)Co(Indene)] complex, J. Chil. Chem. Soc. 63 (2018).
  26. M.B. Robin, P. Day, Mixed Valence Chemistry-A Survey and Classification, Adv. Inorg. Chem. Radiochem. 10 (1967) 247–422. doi:10.1016/S0065-2792(08)60179-X.

Copyright @2019 | Designed by: Open Journal Systems Chile Logo Open Journal Systems Chile Support OJS, training, DOI, Indexing, Hosting OJS

Code under GNU license: OJS PKP