Abstract
Electronic structures of a series oflanthanide complexes with hexafluoroisopropoxide ligands [Ln(OCH(CF3)2)2(μ2-OCH(CF3)2)(DME)]2 (Ln = Ce, Sm, Tm, Yb; DME is dimethoxyethane) were studied by quantum chemical calculations at the density functional theory (DFT) level. Intramolecular C-F→Ln interactions are present in all these compounds. A decrease in the ionic radius of lanthanide in the series from Ce to Yb leads to an increase in the degree of filling of the coordination sphere from 92.9(2) to 97.3(2)%, resulting in a systematic decrease in the delocalization index between lanthanide and fluorine atoms. An experimental-theoretical study of the complexes using a molecular invariom provided an estimate of the energy of Ln⋯F interactions, which also decreases for the complexes of the late lanthanides (Tm, Yb) compared with the complexes of the early lanthanides (Ce, Sm). Geometry optimization of the isolated molecule leads to an increase in the number of non-covalent interactions involving fluorine atoms (F⋯F, F⋯H, and F⋯O) and in their energy compared to the molecular invariom. The topological characteristics of electron density in the coordination sphere of lanthanide atoms determined by quantum chemical calculations are in good agreement with those estimated using the molecular invariom.
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D. C. Bradley, H. Chudzynska, M. E. Hammond, M. B. Hursthouse, M. Motevalli, W. Ruowen, Polyhedron, 1992, 3, 375.
D. R. Click, B. L. Scott, J. G. Watkin, Chem. Commun., 1999, 633.
G. B. Deacon, C. M. Forsyth, Organometallics, 2003, 22, 1349.
S. Banerjee, T. J. Emge, J. G. Brennan, Inorg. Chem., 2004, 43, 6307.
K. Norton, T. J. Emge, J. G. Brennan, Inorg. Chem., 2007, 46, 4060.
D. M. Kuzyaev, R. V. Rumyantsev, G. K. Fukin, M. N. Bochkarev, Russ. Chem. Bull., 2014, 63, 848.
D. Werner, G. B. Deacon, P. C. Junk, R. Anwander, Chem. Eur. J., 2014, 20, 4426.
N. L. Lampland, J. Zhu, M. L. Hovey, B. Jana, A. Ellern, A. D. Sadow, Inorg. Chem., 2015, 54, 6938.
A. A. Maleev, A. A. Fagin, V. A. Ilichev, M. A. Lopatin, A. N. Konev, M. A. Samsonov, G. K. Fukin, M. N. Bochkarev, J. Organome t. Chem., 2013, 747, 126.
L. Armelao, D. B. Dell’Amico, G. Bottaro, P. Falvo, L. Labella, F. Marchetti, D. Parisi, S. Samaritani, Polyhedron, 2015, 85, 770.
K. Norton, G. A. Kumar, J. L. Dilks, T. J. Emge, R. E. Riman, M. G. Brik, J. G. Brennan, Inorg. Chem., 2009, 48, 3573.
A. P. Pushkarev, V. A. Ilichev, A. A. Maleev, A. A. Fagin, A. N. Konev, A. F. Shestakov, R. V. Rumyantzev, G. K. Fukin, M. N. Bochkarev, J. Mater. Chem. C, 2014, 2, 1532.
S. Banerjee, M. D. Romanelli, T. J. Emge, J. G. Brennan, Chem. Mater., 2007, 19, 2937.
S. Banerjee, G. A. Kumar, T. J. Emge, R. E. Riman, J. G. Brennan, Chem. Mater., 2008, 20, 4367.
M. D. Romanelli, PhD (Chem.) Thesis, Graduate School-New Brunswick Rutgers, State University of New Jersey, 2010, 166 pp.
D. M. Kuzyaev, T. V. Balashova, M. E. Burin, G. K. Fukin, R. V. Rumyantcev, A. P. Pushkarev, V. A. Ilichev, I. D. Grishin, D. L. Vorozhtsov, M. N. Bochkarev, Dalton Trans., 2016, 45, 3464.
N. I. Sorokin, B. P. Sobolev, Crystallogr. Repts., 2007, 52, 842.
M. Bralić, N. Radić, S. Brinić, E. Generalić, Talanta, 2001, 55, 581.
J. H. Melman, T. J. Emge, J. G. Brennan, Inorg. Chem., 2001, 40, 1078.
J. H. Melman, C. Rohde, T. J. Emge, J. G. Brennan, Inorg. Chem., 2002, 41, 28.
H. Yin, A. J. Lewis, P. Carroll, E. J. Schelter, Inorg. Chem., 2013, 52, 8234.
B. Liu, T. Roisnel, L. Maron, J.-F. Carpentier, Y. Sarazin, Chem. Eur. J., 2013, 19, 3986.
W. J. Evans, K. J. Forrestal, M. A. Ansari, J. W. Ziller, J. Am. Chem. Soc., 1998, 120, 2180.
M. Zimmermann, K. W. Törnroos, R. Anwander, Angew. Chem., Int. Ed. Engl., 2008, 47, 775.
A. Berkefeld, W. E. Piers, M. Parvez, L. Castro, Chem. Sci., 2013, 4, 2152.
R. V. Rumyantcev, G. K. Fukin, Russ. Chem. Bull., 2017, 66, 1557.
I. A. Guzei, M. Wendt, Dalton Trans., 2006, 3991.
V. A. Blatov, A. P. Shevchenko, D. M. Proserpio, Cryst. Growth Des., 2014, 14, 3576.
R. D. Shannon, Acta Cryst. Section A, 1976, 32(5), 751.
E. Espinosa, E. Molins, C. Lecomte, Chem. Phys. Lett., 1998, 285, 170.
R. V. Rumyantcev, G. K. Fukin, Russ. J. Coord. Chem., 2019, 45, 767.
R. F. Bader, Atoms in Molecules: a Quantum Theory, Oxford University Press, Oxford, 1990.
T. Lu, F. Chen, J. Comp. Chem., 2012, 33, 580.
B. Dittrich, C. M. Wandtke, A. Meents, K. Pröpper, K. C. Mondal, P. P. Samuel, Sk. N. Amin, A. P. Singh, H. W. Roesky, N. Sidhu, ChemPhysChem, 2015, 16, 412.
C. M. Wandtke, M. Weil, J. Simpson, B. Dittrich, Acta Crystallogr. Sect. B Struct. Sci. Cryst. Eng. Mater., 2017, 73, 794.
Y. V. Nelyubina, A. A. Korlyukov, K. A. Lyssenko, I. V. Fedyanin, Inorg. Chem., 2017, 56, 4688.
G. K. Fukin, E. V. Baranov, A. V. Cherkasov, R. V. Rumyantzev, E. A. Kozlova, L. S. Okhlopkova, A. I. Poddel’sky, Russ. Chem. Bull., 2019, 68, 1650.
G. K. Fukin, E. V. Baranov, A. V. Cherkasov, R. V. Rumyantcev, A. N. Artemov, E. V. Sazonova, Russ. J. Coord. Chem., 2019, 45, 680.
G. K. Fukin, A. V. Cherkasov, E. V. Baranov, R. V. Rumyantcev, E. V. Sazonova, A. N. Artemov, Chemistry Select, 2019, 4, 10976.
T. S. Pochekutova, V. K. Khamylov, G. K. Fukin, B. I. Petrov, A. S. Shavyrin, A. V. Arapova, N. M. Lazarev, V. I. Faerman, T. I. Kulikova, E. V. Baranov, N. M. Khamaletdinova, Polyhedron, 2020, 177, 114263.
B. Dittrich, T. Koritsnszky, P. Luger, Angew. Chem. Int. Ed. Engl., 2004, 43, 2718.
B. Dittrich, C.B. Hubschle, P. Luger, M. A. Spackman, Acta Crystallogr. D., 2006, 62, 1325.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford CT, 2013.
K. L. Schuchardt, B. T. Didier, T. Elsethagen, L. Sun, V. Gurumoorthi, J. Chase, J. Li, T. L. Windus, J. Chem. Inf. Model., 2007, 47(3), 1045.
R. Ditchfield, W. J. Hehre, J. A. Pople, J. Chem. Phys., 1971, 54, 724.
W. J. Hehre, R. Ditchfield, J. A. Pople, J. Chem. Phys., 1972, 56, 2257.
P. C. Hariharan, J. A. Pople, Theor. Chim. Acta, 1973, 28, 213.
T. Clark, J. Chandrasekhar, G. W. Spitznagel, P. Von Ragué, J. Comput. Chem., 1983, 4, 294.
M. Dolg, H. Stoll, H. Preuss, J. Chem. Phys., 1989, 90, 1730.
P.-W. Huang, C.-Z. Wang, Q.-Y. Wu, J.-H. Lan, G. Song, Z.-F. Chai, W.-Q. Shi, Phys. Chem. Chem. Phys., 2018, 20, 14031.
M. N. Vo, V. S. Bryantsev, J. K. Johnson, J. A. Keith, Int. J. Quantum Chem., 2017, 118, e25516.
Y.-M. Chen, C.-Z. Wang, Q.-Y. Wu, J.-H. Lan, Z.-F. Chai, C.-M. Nie, W.-Q. Shi, J. Mol. Liq., 2020, 299, 112174.
J. R. Levin, T. Cheisson, P. J. Carroll, E. J. Schelter, Dalton Trans., 2016, 45, 15249.
T. A. Keith, AIMAll (version 17.11.14), TK Gristmill Software, Overland Park KS, USA, 2017 (aim.tkgristmill.com).
F. E. Jorge, L. S. C. Martins, M. L. Franco, Chem. Phys. Lett., 2016, 643, 84.
D. Jayatilaka, D. J. Grimwood, Comput. Sci. ICCS, 2003, 2660, 142.
C. Jelsch, B. Guillot, A. Lagoutte, C. Lecomte, J. Appl. Crystallogr., 2005, 38, 38.
A. Stash, V. Tsirelson, J. Appl. Crystallogr., 2002, 35, 371.
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This study was financially supported by the Russian Science Foundation (Project No. 17-73-20302).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2082—2090, November, 2020.
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Rumyantsev, R.V., Fukin, G.K., Baranov, E.V. et al. Effect of the nature of lanthanide on intramolecular C-F→Ln dative interactions in hexafluoroisopropoxide complexes. Russ Chem Bull 69, 2082–2090 (2020). https://doi.org/10.1007/s11172-020-3003-4
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DOI: https://doi.org/10.1007/s11172-020-3003-4