Transmission of Magnetic Interactions through an Organometallic Coupler: A Novel Family of Metallocene-Substituted α-Nitronyl Aminoxyl Radicals

Inorganic Chemistry

Volumn 37, Issue 18, 1998, Pages 4547-4558

  Jurgens O ^a   Vidal Gancedo, J ^a   Rovira, C ^a   Wurst, K ^b   Sporer, C ^b   Bildstein, B ^b   Schottenberger, H ^b   Jaitner, P ^b   Veciana, J ^a  

^a UNIVERSITAT AUTÒNOMA DE BARCELONA   (Spain)

^b UNIVERSITY OF INNSBRUCK   (Austria)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0039204085     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic980495h     Document Type: Article

References (80)

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56. Although the electrochemistry of substituted ruthenocenes is more complex and less well understood than that of ferrocenes, the first oxidation step may be more reasonably ascribed in this case to the oxidation of the radical part of the molecule, since the oxidation of unsubstituted ruthenocene has been reported to appear as a highly irreversible process at higher oxidizing potentials. See also refs 28, 29, and the following: Denisovitch, L. I.; Zakurin, N. V.; Bezrukova, A. A.; Gubin, S. P. J. Organomet. Chem. 1974, 81, 207. Gale, R. J.; Job, R. Inorg. Chem. 1981, 20, 42-45. Hill, M. G.; Lamanna, W. M.; Mann, K. R. Inorg. Chem. 1991, 30, 4690-4692.
57. Although the electrochemistry of substituted ruthenocenes is more complex and less well understood than that of ferrocenes, the first oxidation step may be more reasonably ascribed in this case to the oxidation of the radical part of the molecule, since the oxidation of unsubstituted ruthenocene has been reported to appear as a highly irreversible process at higher oxidizing potentials. See also refs 28, 29, and the following: Denisovitch, L. I.; Zakurin, N. V.; Bezrukova, A. A.; Gubin, S. P. J. Organomet. Chem. 1974, 81, 207. Gale, R. J.; Job, R. Inorg. Chem. 1981, 20, 42-45. Hill, M. G.; Lamanna, W. M.; Mann, K. R. Inorg. Chem. 1991, 30, 4690-4692.
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62. 35
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68. This spin density distribution is in accordance with experimental data obtained by ESR and NMR spectroscopic measurements and also by polarized neutron diffraction experiments. See: Davis, M. S.; Morokuma, K.; Kreilick, R. W. J. Am. Chem. Soc. 1972, 94, 5588-5592. Neely, J. W.; Hatch, G. F.; Kreilick, R. W. J. Am. Chem. Soc. 1974, 96, 652-656. Zhedulev, A.; Barone, V.; Bonnet, M.; Delley, B.; Grand, A.; Ressouche, E.; Rey, P.; Subra, R.; Schweizer, J. J. Am. Chem. Soc. 1994, 116, 2019-2027. Zhedulev, A.; Ressouche, E.; Schweizer, J.; Turek, P.; Wan, M.; Wang, H. J. Magn. Magn. Mater. 1995, 144, 1441-1442.
69. This spin density distribution is in accordance with experimental data obtained by ESR and NMR spectroscopic measurements and also by polarized neutron diffraction experiments. See: Davis, M. S.; Morokuma, K.; Kreilick, R. W. J. Am. Chem. Soc. 1972, 94, 5588-5592. Neely, J. W.; Hatch, G. F.; Kreilick, R. W. J. Am. Chem. Soc. 1974, 96, 652-656. Zhedulev, A.; Barone, V.; Bonnet, M.; Delley, B.; Grand, A.; Ressouche, E.; Rey, P.; Subra, R.; Schweizer, J. J. Am. Chem. Soc. 1994, 116, 2019-2027. Zhedulev, A.; Ressouche, E.; Schweizer, J.; Turek, P.; Wan, M.; Wang, H. J. Magn. Magn. Mater. 1995, 144, 1441-1442.
70. This spin density distribution is in accordance with experimental data obtained by ESR and NMR spectroscopic measurements and also by polarized neutron diffraction experiments. See: Davis, M. S.; Morokuma, K.; Kreilick, R. W. J. Am. Chem. Soc. 1972, 94, 5588-5592. Neely, J. W.; Hatch, G. F.; Kreilick, R. W. J. Am. Chem. Soc. 1974, 96, 652-656. Zhedulev, A.; Barone, V.; Bonnet, M.; Delley, B.; Grand, A.; Ressouche, E.; Rey, P.; Subra, R.; Schweizer, J. J. Am. Chem. Soc. 1994, 116, 2019-2027. Zhedulev, A.; Ressouche, E.; Schweizer, J.; Turek, P.; Wan, M.; Wang, H. J. Magn. Magn. Mater. 1995, 144, 1441-1442.
71. The variance of the zfs parameters within the given ±10° intervals is very large, i.e., 20% for D′ and 53% for E′ in 2 (M = Fe), and 7% for D′ and 60% for E′ in 2 (M = Ru), giving an idea of the precision of this structural assignment.
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73. For such a simulation it was assumed that the g and D tensors are collinear for diradicals 2 (M = Fe, Ru).
74. Carlin, R. L. Magnetochemistry; Springer-Verlag: Berlin, 1986; pp 71-77.
75. s = ±2 signal at low temperatures since the signal of the predominating conformer with strong antiferromagnetic interactions becomes weaker.
76. eff = T - θ. See: Carlin, R. L. Magnetochemistry; Springer-Verlag: Berlin, 1986; p 88.
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