Abstract
The complexes \({\text{[P}}{{{\text{h}}}_{{\text{3}}}}{\text{PR]}}_{{\text{2}}}^{{\text{ + }}}\)[HfCl6]2–, where R = Et (I), CH2C6H4CN-4 (II), or CH2C6H4F-4 (III), have been synthesized by the reaction between hafnium tetrachloride and tetraorganylphosphonium chlorides in acetonitrile and structurally characterized. According to X-ray diffraction data, the phosphorus atoms in tetraorganylphosphonium cations have a distorted tetrahedral coordination: the CPC angles are 108.07(8)°–110.89(8)° (I), 105.0(3)°–113.8(3)° (II), and 99.5(4)°–115.7(4)° (III), and the P–С bond lengths are 1.7958(17)–1.8042(19) Å (I), 1.758(6)–1.834(6) Å (II), and 1.714(8)–1.930(10) Å (III). In the centrosymmetric octahedral anions [HfCl6]2– of complex I, the Hf–Cl distances are 2.4549(8)–2.4584(10) Å. In complexes II and III, the octahedral configuration of anions is distorted: the trans-ClHfCl angles are 177.23(13)°–180.00° and 177.73(9)°, 178.07(10)°, 178.84(9)°, respectively, and the Hf–Cl bonds are 2.3949(18)–2.4976(17) Å (II) and 2.411(2)–2.527(5) Å (III). The structural organization of crystals is formed by weak hydrogen bonds Cl⋅⋅⋅Н–С (2.75–2.92, 2.63–2.94, and 2.75–2.83 Å) between anions and cations.
Similar content being viewed by others
REFERENCES
K. Ruhlandt-Senge, A.-D. Bacher, and U. Muller, Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 46, 1925 (1990). https://doi.org/10.1107/S0108270190004243
M. Schormann, S. Garratt, D. L. Hughes, et al., J. Am. Chem. Soc. 124, 11266 (2002). https://doi.org/10.1021/ja026443f
P. V. Andreev, E. V. Lobanova, and P. D. Drozhilkin, Vestn. Yuzhn. Ural. Gos. Univ., Ser. Khim. 11 (4), 26 (2019). https://doi.org/10.14529/chem190403
C. Hagfeldt, V. Kessler, and I. Persson, New J. Chem. 27, 850 (2003). https://doi.org/10.1039/B210969G
M. Dotterl, I. Haas, and H. G. Alt, Z. Anorg. Allg. Chem. 637, 1502 (2011). https://doi.org/10.1002/zaac.2011002446
B. Neumuller and K. Dehnicke, Z. Anorg. Allg. Chem. 630, 2576 (2004). https://doi.org/10.1002/zaac.200400370
S. G. Minasian, K. S. Boland, R. K. Feller, et al., Inorg. Chem. 51, 5728 (2012). https://doi.org/10.1021/ic300179d
S. D. Reid, A. L. Hector, W. Levason, et al., Dalton Trans., 4769 (2007). https://doi.org/10.1039/B708809D
F. Calderazzo, I. Ferri, G. Pampaloni, and S. Troyanov, J. Organomet. Chem. 518, 189 (1996). https://doi.org/10.1016/0022-328X(96)06194-3
M. Schormann, S. Garratt, and M. Bochmann, Organometallics 24, 1718 (2005). https://doi.org/10.1021/om0491692
F. Calderazzo, P. Pallavicini, G. Pampaloni, and P. F. Zanazzi, J. Chem. Soc., Dalton Trans., 2743 (1990). https://doi.org/10.1039/DT9900002743
S. K. Roymuhury, D. Chakraborty, and V. Ramkumar, New J. Chem. 39, 5218 (2015). https://doi.org/10.1039/C5NJ00486A
SMART and SAINT-Plus: Data Collection and Processing Software for the SMART System, Versions 5.0 (Bruker, Madison, Wisconsin, 1998).
Bruker (1998). SHELXTL/PC: An Integrated System for Solving, Refining and Displaying Crystal Structures from Diffraction Data, Versions 5.10 (Bruker, Madison, Wisconsin, 1998).
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, et al., J. Appl. Crystallogr. 42, 339 (2009). https://doi.org/10.1107/S0021889808042726
V. V. Sharutin, O. K. Sharutina, and E. V. Lobanova, Russ. J. Inorg. Chem. 63, 1549 (2018). https://doi.org/10.1134/S0036023618120197
V. V. Sharutin, O. K. Sharutina, N. M. Tarasova, and O. S. Eltsov, Russ. Chem. Bull. 68 (1), 24 (2019). https://doi.org/10.1007/s11172-019-2411-9
V. V. Sharutin, O. K. Sharutina, N. M. Tarasova, et al., Izv. Vyssh. Uchebn. Zaved. 62 (6), 36 (2019). https://doi.org/10.6060/ivkkt.20196206.5885
E. Pretsch, P. Bulmann, and K. Affolter, Structure Determination ofOrganic Compounds (Springer, Berlin, 2000; Mir, Moscow, 2006) [in Russian].
Cambridge Crystallographic Data Center, 2018.
S. S. Batsanov, Zh. Neorg. Khim. 36, 3015 (1991).
Yu. V. Zefirov and P. M. Zorkii, Usp. Khim. 64, 446 (1995). https://doi.org/10.1070/RC1995v064n05ABEH000157
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
The authors declare that they have no conflict of interests.
Additional information
Translated by E. Glushachenkova
Rights and permissions
About this article
Cite this article
Sharutin, V.V., Sharutina, O.K. & Lobanova, E.V. Hafnium Complexes \([{\mathbf{P}}{{{\mathbf{h}}}_{{\mathbf{3}}}}{\mathbf{PR}}]_{{\mathbf{2}}}^{ + }\)[HfCl6]2–, where R = Et, CH2C6H4CN-4, or CH2C6H4F-4: Synthesis and Structure. Russ. J. Inorg. Chem. 65, 870–873 (2020). https://doi.org/10.1134/S0036023620060200
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0036023620060200