Synthesis, X-ray crystal structures and properties of chromium complexes with semiquinonate and catecholate

Abstract

The reaction of tris-tetrahalogeno-o-benzosemiquinonate chromium(III) complexes, [Cr^III(X₄SQ)₃] (X = Cl 1a or Br 1b), with bis(cyclopentadienyl) cobalt [Co^IICp₂], tetramethyltetraselenafulvalene (TMTSF ) and tetrakis(methylsulfanyl)tetrathiafulvalene (TMT-TTF) afforded four charge-transfer compounds, [Co^IIICp₂][Cr^III(X₄SQ)₂(X₄Cat)] (X = Cl 2a or Br 2b), [TMT-TTF ][Cr^III(Br₄SQ)₂(Br₄Cat)] 3b and [TMTSF ][Cr^III(Br₄SQ)₂(Br₄Cat)] 4b, where Cat is catecholate. The paramagnetic [Cr^III(X₄SQ)₂(X₄Cat)]^– complexes are commonly formed by cocrystallization with a diamagnetic [Co^IIICp₂]⁺ cation for 2a·C₆H₆ and 2b, and paramagnetic TMT-TTF^˙+ and TMTSF^˙+ cations for 3b·C₆H₅CH₃ and 4b·2CH₂Cl₂, respectively. The one-electron reduced complexes, [Cr^III(X₄SQ)₂(X₄Cat)]^–, with two semiquinonate and one catecholate ligands were isolated and crystallographically characterized. The crystal structures of 2a·C₆H₆ and 3b·C₆H₅CH₃ consist of alternating stacks of cations and anionic complexes, which form one-dimensional column structures. On the other hand, the anionic complexes in 4b·2CH₂Cl₂ form a hexagonal honeycomb network, whose cavities are occupied by the dimerized cation molecules. The temperature dependence of the magnetic susceptibilities reveals that all the [Cr^III(X₄SQ)₂(X₄Cat)]^– complexes are in a ground state of S = 1/2, which results from the intramolecular antiferromagnetic interaction between Cr^III(d³) and two semiquinonates. In addition, 3b and 4b have a contribution of the paramagnetic TMT-TTF^˙+ (3b) and TMTSF^˙+ (4b) cations. In all compounds weak intermolecular magnetic interactions were recognized from the decrease of the χ_mT values at low temperature.

References

1. (a) C. G. Pierpont and C. W. Lange, Prog. Inorg. Chem., 1994, 41, 331; (b) C. G. Pierpont and R. M. Buchanan, Coord. Chem. Rev., 1981, 38, 45.
2. (a) D. M. Adams, L. Noodleman and D. N. Hendrickson, Inorg. Chem., 1997, 36, 3966; (b) O.-S. Jung and C. G. Pierpont, J. Am. Chem. Soc., 1994, 116, 2229; (c) C. Roux, D. M. Adams, J. P. Itié, A. Polian, D. N. Hendrickson and M. Verdaguer, Inorg. Chem., 1996, 35, 2846.
3. (a) H. H. Downs, R. M. Buchanan and C. G. Pierpont, Inorg. Chem., 1979, 18, 1736; (b) S. R. Sofen, D. C. Ware, S. R. Cooper and K. N. Raymond, Inorg. Chem., 1979, 18, 234.
4. (a) C. G. Pierpont and H. H. Downs, J. Am. Chem. Soc., 1976, 98, 4834; (b) K. N. Raymond, S. S. Isied, L. D. Brown, F. R. Fronczek and J. H. Nibert, J. Am. Chem. Soc., 1976, 98, 1767; (c) R. M. Buchanan, S. L. Kessel, H. H. Downs, C. G. Pierpont and D. N. Hendrickson, J. Am. Chem. Soc., 1978, 100, 7894; (d) R. M. Buchanan, H. H. Downs, W. B. Shorthill, C. G. Pierpont, S. L. Kessel and D. N. Hendrickson, J. Am. Chem. Soc., 1978, 100, 4318; (e) D. J. Gordon and R. F. Fenske, Inorg. Chem., 1982, 21, 2907.
5. C. G. Pierpont, H. H. Downs and T. G. Rukavina, J. Am. Chem. Soc., 1974, 96, 5573.
6. (a) G. Saito, T. Enoki, H. Inokuchi, H. Kumagai, C. Katayama and J. Tanaka, Mol. Cryst. Liq. Cryst., 1985, 120, 345; (b) K. Imaeda, T. Enoki, T. Mori, P. Wu, M. Kobayashi and H. Inokuchi, Synth. Met., 1987, 19, 721; (c) H. Endres, Acta Crystallogr., Sect. C, 1987, 43, 439; (d) T. Enoki, J. Yamaura, N. Sugiyasu, K. Suzuki and G. Saito, Mol. Cryst. Liq. Cryst., 1993, 233, 325; (e) K. Bechgaard, C. S. Jacobsen, K. Mortensen, H. J. Pedersen and N. Thorup, Solid State Commun., 1980, 33, 1119; (f) A. E. Underhill, J. S. Tonge, P. I. Clemenson, H.-H. Wang and J. M. Williams, Mol. Cryst. Liq. Cryst., 1985, 125, 439; (g) S. Triki, L. Ouahab, J. Padiou and D. Grandjean, J. Chem. Soc., Chem. Commun., 1989, 1068.
7. O. Kahn, Molecular Magnetism, VCH, New York, 1993.
8. SIR 92, A. Altomare, M. C. Burla, M. Camalli, M. Cascarano, C. Giacovazzo, A. Guagliardi and G. Pilidori, J. Appl. Crystallogr., 1994, 27, 435.
9. DIRDIF 94, P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, R. de Gelder, R. Israel and J. M. M. Smits, Technical Report of the Crystallography Laboratory, University of Nijmegen, 1994.
10. TEXSAN, Crystal Structure Analysis Package, Molecular Structure Corporation, The Woodlands, TX, 1985 and 1992.
11. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
12. (a) W. Bunder and E. Weiss, J. Organomet. Chem., 1975, 92, 65; (b) D. W. Kemmitt and D. R. Russell, Comprehensive Organometallic Chemistry, eds. G. A. Wilkinson, F. G. A. Stone and E. W. Abel, Pergamon, Oxford, 1982.
13. (a) T. Mori, P. Wu, K. Imaeda, T. Enoki and H. Inokuchi, Synth. Met., 1987, 19, 545; (b) C. Katayama, M. Honda, H. Kumagai, K. Tanaka, G. Saito and H. Inokuchi, Bull. Chem. Soc. Jpn., 1985, 58, 2272; (c) K. Honda, M. Goto, M. Kurahashi, H. Anzai, M. Tokumoto and T. Ishiguro, Bull. Chem. Soc. Jpn., 1988, 61, 588; (d) T. J. Kistenmacher, T. J. Emge, P. Shu and D. O. Cowan, Acta Crystallogr., Sect. B, 1979, 35, 772; (e) L. Ouahab, J. Padiou, D. Grandjean, C. Garrigou-Lagrange, P. Delhaes and M. Bencharif, J. Chem. Soc., Chem. Commun., 1989, 1038; (f) N. Thorup, G. Rindorf and H. Soling, Acta Crystallogr., Sect. B, 1981, 37, 1236; (g) S. Triki, L. Ouahab, J. -F. Halet, O. Peña, J. Padiou, D. Grandjean, C. Garrigou-Lagrange and P. Delhaes, J. Chem. Soc., Dalton Trans., 1992, 1217.
14. P. Guionneau, C. J. Kepert, G. Bravic, D. Chasseau, M. R. Truter, M. Kurmoo and P. Day, Synth. Met., 1997, 86, 1973.
15. R. M. Buchanan, J. Claflin and C. G. Pierpont, Inorg. Chem., 1983, 22, 2552.
16. (a) R. M. Buchanan and C. G. Pierpont, J. Am. Chem. Soc., 1980, 102, 4951; (b) A. S. Attia, S. Bhattacharya and C. G. Pierpont, Inorg. Chem., 1995, 34, 4427; (c) O.-S. Jung, D. H. Jo, Y.-A. Lee, B. J. Conklin and C. G. Pierpont, Inorg. Chem., 1997, 36, 19; (d) O.-S. Jung and C. G. Pierpont, Inorg. Chem., 1994, 33, 2227.
17. M. E. Cass, D. L. Greene, R. M. Buchanan and C. G. Pierpont, J. Am. Chem. Soc., 1983, 105, 2680.
18. C. W. Lange and C. G. Pierpont, Inorg. Chim. Acta, 1997, 263, 219.
19. A. S. Attia and C. G. Pierpont, Inorg. Chem., 1998, 37, 3051.
20. A. S. Attia and C. G. Pierpont, Inorg. Chem., 1997, 36, 6184; 1995, 34, 1172.
21. C. Bellitto, M. Bonamico, V. Fares and P. Serino, Inorg. Chem., 1996, 35, 4070; L. J. Pace, A. Ulman and J. A. Ibers, Inorg. Chem., 1982, 21, 199; J. S. Kasper and L. V. Interrante, Acta Crystallogr., Sect. B, 1976, 32, 2914.
22. S. Decurtins, H. W. Schmalle, H. R. Oswald, A. Linden, J. Ensling, P. Gütlich and A. Hauser, Inorg. Chim. Acta, 1994, 216, 65; H. Tamaki, Z. J. Zhong, N. Matsumoto, S. Kida, M. Koikawa, N. Achiwa, Y. Hashimoto and H. Okawa, J. Am. Chem. Soc., 1992, 114, 6974; C. J. Nuttall, C. Bellitto and P. Day, J. Chem. Soc., Chem. Commun., 1995, 1513.
23. M. W. Lynch, M. Valentine and D. N. Hendrickson, J. Am. Chem. Soc., 1982, 104, 6982; M. E. Cass, N. R. Gordon and C. G. Pierpont, Inorg. Chem., 1986, 25, 3962.
24. O.-S. Jung, D. W. Jo, Y.-A. Lee, H. K. Chae and Y. S. Sohn, Bull. Chem. Soc. Jpn., 1996, 69, 2211.
25. J. M. Williams, J. R. Ferraro, R. J. Thorn, K. D. Carlson, U. Geisen, H. H. Wang, A. M. Kini and M.-H. Whangbo, Organic Superconductors (including Fullerenes), Prentice Hall, Englewood Cliffs, NJ, 1992.
26. (a) D. E. Wheeler and J. K. McCusker, Inorg. Chem., 1998, 37, 2296; (b) C. Benelli, A. Dei, D. Gatteschi, H. U. Güdel and D. Pardi, Inorg. Chem., 1989, 28, 3089.