How Good is Clathrochelate Framework in Facilitating Long-Range Electron-Transfer? Case Study of the Ferrocenylboron-Capped Iron(II) Clathrochelate

Forrest Dalbec,^a Alex J. King,^a Irina G. Belaya,^b Yan Z. Voloshin,^b@1 and Victor N. Nemykin^c@2

^aDepartment of Chemistry & Biochemistry, University of Minnesota Duluth, MN 55812 Duluth, USA

^bNesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991 Moscow, Russia

^cDepartment of Chemistry, University of Manitoba, MB R3T 2N2 Winnipeg, Canada

^@1Corresponding author E-mail: voloshin@ineos.ac.ru

^@2Corresponding author E-mail: Victor.Nemykin@umanitoba.ca

DOI: 10.6060/mhc180278v

Macroheterocycles 2018 11(3) 246-250

A potential long-range electronic coupling between two apical ferrocenyl substituents in the clathrochelate molecule FeDm₃(BFc)₂ (where Dm^2– is dimethylglyoximate dianion) was studied using the electrochemical and the spectroelectrochemical methods with a low ion-pairing ability TBAF {(NBu₄)(B(C₆F₅)₄)} electrolyte. Experimental data are suggestive of a rather poor ability of the quasiaromatic polyazomethine clathrochelate framework to facilitate an intramolecular long-distance electron transfer. Experimental observations were correlated with the theoretical results obtained by Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) calculations.

References:

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1. Voloshin Y.Z., Kostromina N.A., Krämer R. Clathrochelates: Synthesis, Structure and Properties. Amsterdam: Elsevier, 2002. 432 p.

2. Voloshin Y.Z., Belaya I.G., Krämer R. Cage metal complexes: Clathrochelates Revisited. Heidelberg: Springer, 2017. 467 p.
https://doi.org/10.1007/978-3-319-56420-3

3. Dudkin S.V., Erickson N.R., Vologzhanina A.V., Novikov V.V., Rhoda H.M., Holstrom C.D., Zatsikha Y.V., Yusubov M.S., Voloshin Y.Z., Nemykin V.N. Inorg. Chem. 2016, 55, 11867–11882.
https://doi.org/10.1021/acs.inorgchem.6b01936

4. Volosin Y.Z., Kron T.E., Belsky V.K., Zavodnik V.E., Maletin Y.A., Kozachkov S.G. J. Organomet. Chem. 1997, 536-537, 207–216.
https://doi.org/10.1016/S0022-328X(96)06776-9

5. Gaussian 09, Revision D.1, Frisch M.J., Trucks G.W., Schlegel H.B., Scuseria G.E., et al Gaussian, Inc., Wallingford CT, 2009.

6. Tenderholt A.L. QMForge, Version 2.1. Stanford University, Stanford, CA, USA.

7. (a) Becke A.D. J. Chem. Phys. 1993, 98, 5648–5652.
https://doi.org/10.1063/1.464913
(b) Lee C., Yang W., Parr R.G. Phys. Rev. B 1988, 37, 785–789.
https://doi.org/10.1103/PhysRevB.37.785

8. Wachters A.J.H. J. Chem. Phys. 1970, 52, 1033–1036.
https://doi.org/10.1063/1.1673095

9. McLean A.D., Chandler G.S. J. Chem. Phys. 1980, 72, 5639–5648.
https://doi.org/10.1063/1.438980

10. Scalmani G., Frisch M.J., Mennucci B., Tomasi J., Cammi R., Barone V. J. Chem. Phys. 2006, 124, 094107:1–15.
https://doi.org/10.1063/1.2173258

11. (a) Geiger W.E., Connelly N.G. Adv. Organomet. Chem. 1985, 24, 87–130.
https://doi.org/10.1016/S0065-3055(08)60414-1
(b) Santi S., Bisello A., Cardena R., Donoli A. Dalton Trans. 2015, 44, 5234–5257.
https://doi.org/10.1039/C4DT03581J
(c) Hildebrandt A., Schaarschmidt D., Claus R., Lang H. Inorg. Chem. 2011, 50, 10623–10632.
https://doi.org/10.1021/ic200926z
(d) Hildebrandt A., Schaarschmidt D., Lang H. Organometallics 2011, 30, 556–563.
https://doi.org/10.1021/om100914m

12. (a) Goetsch W.R., Solntsev P.V., Van Stappen C., Purchel A.A., Dudkin S.V., Nemykin V.N. Organometallics 2014, 33, 145–157.
https://doi.org/10.1021/om400901w
(b) Solntsev P.V., Dudkin S.V., Sabin J.R., Nemykin V.N. Organometallics 2011, 30, 3037–3046.
https://doi.org/10.1021/om2001266
(c) Sabin J.R., Varzatskii O.A., Voloshin Y.Z., Starikova Z.A., Novikov V.V., Nemykin V.N. Inorg. Chem. 2012, 51, 8362–8372.
https://doi.org/10.1021/ic3008798
(d) Nemykin V.N., Basu P. Inorg. Chem. 2003, 42, 4046–4056.
https://doi.org/10.1021/ic0262942

13. Pittman C.U. Jr., Lai J.C., Vanderpool D.P. Macromolecules 1970, 3, 105–107.
https://doi.org/10.1021/ma60013a024

14. Robin M.B., Day P. Advances in Radiochemistry 1967, 10, 247–422.
https://doi.org/10.1016/S0065-2792(08)60179-X

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How Good is Clathrochelate Framework in Facilitating Long-Range Electron-Transfer? Case Study of the Ferrocenylboron-Capped Iron(II) Clathrochelate

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