Abstract
Zirconium fluoro complexes with phosphoryl-containing bases (L) have been synthesized by the reaction of a suspension of ZrF4(dmso)2 in toluene with an excess of Ph3PO or Bu3PO, as well as (Me2N)3PO in CH2Cl2. The composition and structure of the complexes in CH2Cl2 solutions have been studied by 19F NMR in the temperature range 293–203 K. Phosphine oxides are substituted for dmso to form mainly cis-tetrafluoro species, insignificant amounts of trans-tetrafluoro species, and mer- and fac-[ZrF3L3]+ complexes. In addition to these species, the reaction with Bu3PO yields the dimeric oxo complex (µ-O)[ZrF3(Bu3PO)2]2. Hydrolysis of fluoro complexes in CH2Cl2 with the use of an NBu4OH solution in iso-PrOH does not lead to oxo and hydroxo complexes: first, the [ZrF5L]– complex is formed, and the final hydrolysis product is ZrF6 2-. The fine structure of 19F NMR resonance lines for the zirconium fluoride compounds [ZrF5L]–, cis- [ZrF4L2], dimeric oxo complex, and mer-[ZrF3L3]+ in organic solvents has been observed for the first time, which makes it possible to reliably identify the composition and structure of the zirconium coordination polyhedron in the complexes under consideration.
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References
Yu. A. Buslaev, V. P. Tarasov, and S. P. Petrosyants, Zh. Strukt. Khim.., No. 2, 198 (1968).
S. O. Gerasimova, S. A. Polishchuk, L. M. Avkhutskii, et al., Koord. Khim. 7, 884 (1981).
B. N. Chernyshov, N. A. Didenko, N. G. Obukhova, et al., Koord. Khim. 15, 1199 (1989).
N. W. Alcock, W. Errington, S. L. Golby, et al., Acta Crystallogr. Sect. C 50, 226 (1994).
E. G. Il’in, H. W. Roesky, G. G. Aleksandrov, et al., Dokl. Phys. Chem. 355, 229 (1997).
E. G. Il’in, V. V. Kovalev, G. G. Aleksandrov, and I. Grenthe, Dokl. Chem. 401, 42 (2005).
E. G. Il’in, G. B. Nikiforov, and G. G. Aleksandrov, Dokl. Chem. 400, 7 (2005).
E. G. Il’in, V. V. Kovalev, G. G. Aleksandrov, and A. V. Sergeev, Dokl. Chem. 398, 200 (2004).
E. G. Il’in, V. V. Kovalev, G. G. Aleksandrov, et al., Dokl. Chem. 375, 265 (2000).
E. G. Il’in and V. V. Kovalev, Dokl. Chem. 402, 95 (2005).
E. G. Il’in, V. V. Kovalev, and G. G. Aleksandrov, Dokl. Phys. Chem. 405, 224 (2005).
A. G. Beirakhov, I. M. Orlova, E. G. Il’in, et al., Zh. Neorg. Khim. 52, 34 (2007).
S. L. Benjamin, W. Lewason, D. Pugh, et al., Dalton Trans. 41, 12548 (2012).
E. G. Il’in and Yu. A. Buslaev, Dokl. Akad. Nauk SSSR 246, 1165 (1979).
S. L. Benjamin, W. Lewason, and G. Reid, Chem. Soc. Rev. 42, 1460 (2013).
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Original Russian Text © V.V. Kovalev, E.G. Il’in, 2016, published in Zhurnal Neorganicheskoi Khimii, 2016, Vol. 61, No. 1, pp. 67–73.
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Kovalev, V.V., Il’in, E.G. Synthesis and speciation of zirconium tetrafluoride complexes with phosphoryl-containing bases Ph3PO, Bu3PO and (Me2N)3PO in solutions. Russ. J. Inorg. Chem. 61, 63–68 (2016). https://doi.org/10.1134/S0036023616010125
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DOI: https://doi.org/10.1134/S0036023616010125