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Volumn 130, Issue 30, 2008, Pages 9859-9870

Cymantrene radical cation family: Spectral and structural characterization of the half-sandwich analogues of ferrocenium ion

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Indexed keywords

ARSENIC COMPOUNDS;

EID: 48249132028     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja801930q     Document Type: Article
Times cited : (60)

References (136)
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    • (1982) Comprehensive Organometallic Chemistry , vol.4 , pp. 123-132
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    • (Original preparation) Piper, T. S.; Cotton, F. A.; Wilkinson, G. J. Inorg. Nucl. Chem. 1955, 1, 165.
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    • Chiral synthesis: (f) Ferber, B.; Top, S.; Jaouen, G. J. Organomet. Chem. 2004, 689, 4872.
    • Chiral synthesis: (f) Ferber, B.; Top, S.; Jaouen, G. J. Organomet. Chem. 2004, 689, 4872.
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    • Leading references to the literature of ferrocenyl redox tags are: (a) Cuffe, L.; Hudson, R. D. A.; Gallagher, J. F.; Jennings, S.; McAdam, C. J.; Connelly, R. B. T.; Manning, A. R.; Robinson, B. H.; Simpson, J. Organometallics 2005, 24, 2051.
    • Leading references to the literature of ferrocenyl redox tags are: (a) Cuffe, L.; Hudson, R. D. A.; Gallagher, J. F.; Jennings, S.; McAdam, C. J.; Connelly, R. B. T.; Manning, A. R.; Robinson, B. H.; Simpson, J. Organometallics 2005, 24, 2051.
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    • These results and otherwise unpublished data have been discussed by: (c) van Dam, H.; Oskam, A. In Transition Metal Chemistry; Melson, G. A., Figgis, B. N., Eds.; Marcel Dekker, Inc.: New York, 1985; pp 174 ff.
    • These results and otherwise unpublished data have been discussed by: (c) van Dam, H.; Oskam, A. In Transition Metal Chemistry; Melson, G. A., Figgis, B. N., Eds.; Marcel Dekker, Inc.: New York, 1985; pp 174 ff.
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    • Adding to the pseudo-octahedral model is the fact that the lowest unfilled orbitals in cymantrene and ferrocene are nearly degenerate sets of e1″-type cyclopentadienyl π-orbitals that are metal-antibonding
    • 1″-type cyclopentadienyl π-orbitals that are metal-antibonding.
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    • Wilkinson, G, Stone, F. G. A, Abel, E. W, Eds, Pergamon Press: Oxford
    • Mingos, D. M. P. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: Oxford, 1982; Vol. 3, pp 28-46.
    • (1982) Comprehensive Organometallic Chemistry , vol.3 , pp. 28-46
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    • Reference 16, p 385
    • Reference 16, p 385.
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    • Under normal experimental conditions, the maximum CV time scale is approximately 10 s.
    • Under normal experimental conditions, the maximum CV time scale is approximately 10 s.
  • 51
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    • The ESR spectrum assigned to 1+ from a solution of bulk-electrolyzed cymantrene (ref 12) almost certainly arose from a decomposition product. As shown in the present work, the cymantrene radical cation is ESR-silent under the fluid room-temperature conditions employed in that work and the spectral characteristics (〈g〈, 2.015, 〈A〉Mn, 92.5 G) are typically found in Mn(II) solvento complexes. A similar spectrum assigned to a cymantrenyl-based radical cation observed after iodine oxidation of Mn(η5-C 5H4Me)(CO)2(C(O)-ferrocenyl, see ref 33, 〈g〉, 2.037, 〈A〉Mn, 91.6 G) is also likely to have arisen from radical decomposition
    • Mn = 91.6 G) is also likely to have arisen from radical decomposition.
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    • Manuel, T. A. Adv. Organomet. Chem. 1965, 3, 181. (see especially p 221)
    • (b) Manuel, T. A. Adv. Organomet. Chem. 1965, 3, 181. (see especially p 221)
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    • + is not quantitatively reduced back to 1 due to its decomposition.
    • + is not quantitatively reduced back to 1 due to its decomposition.
  • 98
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    • This value of 40% Cr spin is based on the correction of the data in ref 50 by Rieger in ref 53
    • This value of 40% Cr spin is based on the correction of the data in ref 50 by Rieger in ref 53.
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    • An exception to this generalization is that fluid spectra may be obtained for high-symmetry radicals having a 2A ground state (see ref 59 as well as (a) Elschenbroich, C, Mockel, R, Vasil'kov, A, Metz, B, Harms, K. Eur. J. Inorg. Chem. 1998, 10, 1391
    • 2A ground state (see ref 59 as well as (a) Elschenbroich, C.; Mockel, R.; Vasil'kov, A.; Metz, B.; Harms, K. Eur. J. Inorg. Chem. 1998, 10, 1391).
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    • An exception to this generalization is that the four observed parallel features of 1+ increased in width going from lower-to-higher field in a spectrum recorded at 10 K
    • + increased in width going from lower-to-higher field in a spectrum recorded at 10 K.
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    • + in solution at room temperature under NMR conditions, a small amount of 1 was apparently present in this sample.
    • + in solution at room temperature under NMR conditions, a small amount of 1 was apparently present in this sample.
  • 128
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    • 5L, L = CO or donor ligand.
    • 5L, L = CO or donor ligand.
  • 129
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    • 3 (R = Me or Et). See refs 9, 11, 12, 25, 34, and 35 as well as:(a) Yeung, L. K.; Kim, J. E.; Chung, Y. K.; Rieger, P. H.; Sweigart, D. A. Organometallics 1996, 15, 3891.
    • 3 (R = Me or Et). See refs 9, 11, 12, 25, 34, and 35 as well as:(a) Yeung, L. K.; Kim, J. E.; Chung, Y. K.; Rieger, P. H.; Sweigart, D. A. Organometallics 1996, 15, 3891.
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    • 3 were carried out first by photolytic substitution of CO by a strong donor such as pyridine, followed by electrocatalytic substitution of pyridine by a slightly weaker donor ligand such as phosphine.
    • 3 were carried out first by photolytic substitution of CO by a strong donor such as pyridine, followed by electrocatalytic substitution of pyridine by a slightly weaker donor ligand such as phosphine.
  • 133
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    • 1/2 value of-0.25 V vs ferrocene.
    • 1/2 value of-0.25 V vs ferrocene.
  • 134
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    • For early references to the group VI analogues, see: a
    • For early references to the group VI analogues, see: (a) Adams, R. D.; Collins, D. E.; Cotton, F. A. J. Am. Chem. Soc. 1974, 96, 749.
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    • A list of 26 references on this topic may be found in ref 41a
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