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Volumn 46, Issue 32, 2007, Pages 6132-6136

Bis(1,2,3,4-η4-anthracene)ferrate(1-): A paramagnetic homoleptic polyarene transition-metal anion

Author keywords

Arene ligands; Diene ligands; Iron; Negative valent complexes; Sandwich complexes

Indexed keywords

BUTADIENE; COMPLEXATION; METAL COMPLEXES; NEGATIVE IONS; PARAMAGNETIC MATERIALS;

EID: 34548126524     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200701353     Document Type: Article
Times cited : (61)

References (71)
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    • Wilke's remarkable (trans,trans,trans-1,5,9-cyclododecatriene)- nickel(0) was the first storable source of a transition-metal atom and due to its high reactivity is often called naked nickel. See: C. Elschenbroich, Organometallics, 3rd edition, Wiley-VCH, Weinheim, 2006, pp. 397, 694.
    • Wilke's remarkable (trans,trans,trans-1,5,9-cyclododecatriene)- nickel(0) was the first storable source of a transition-metal atom and due to its high reactivity is often called "naked nickel." See: C. Elschenbroich, Organometallics, 3rd edition, Wiley-VCH, Weinheim, 2006, pp. 397, 694.
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    • 2+: E. O. Fischer, C. Elschenbroich, C. G. Kreiter, J. Organomet. Chem. 1967, 7, 481;
    • 2+: E. O. Fischer, C. Elschenbroich, C. G. Kreiter, J. Organomet. Chem. 1967, 7, 481;
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    • 2], M = Cr, Mo: E. P. Kündig, P. L. Timms, J. Chem. Soc. Chem. Commun. 1977, 912;
    • 2], M = Cr, Mo: E. P. Kündig, P. L. Timms, J. Chem. Soc. Chem. Commun. 1977, 912;
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    • 2]: C. Elschenbroich, R. Möckel, Angew. Chem. 1977, 89, 908;
    • 2]: C. Elschenbroich, R. Möckel, Angew. Chem. 1977, 89, 908;
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    • 2]: C. Elschenbroich, R. Möckel, E. Bilger, Z. Naturforsch. B 1984, 39, 375.
    • 2]: C. Elschenbroich, R. Möckel, E. Bilger, Z. Naturforsch. B 1984, 39, 375.
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    • L = anthracene: W. W. Brennessel, V. G. Young, Jr., J. E. Ellis, Angew. Chem. 2002, 114, 1259;
    • a) L = anthracene: W. W. Brennessel, V. G. Young, Jr., J. E. Ellis, Angew. Chem. 2002, 114, 1259;
  • 15
  • 16
    • 34548142377 scopus 로고    scopus 로고
    • L = naphthalene: W. W. Brennessel, V. G. Young, Jr., J. E. Ellis, Angew. Chem. 2006, 118, 7426;
    • b) L = naphthalene: W. W. Brennessel, V. G. Young, Jr., J. E. Ellis, Angew. Chem. 2006, 118, 7426;
  • 17
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    • 2].
    • 2].
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    • A claim for the existence of bis(naphthalene)iron(0) remains unverified: P. D. Morand, C. G. Francis, Inorg. Chem. 1985, 4, 1653.
    • A claim for the existence of bis(naphthalene)iron(0) remains unverified: P. D. Morand, C. G. Francis, Inorg. Chem. 1985, 4, 1653.
  • 21
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    • 3]: T. A. Manuel, Inorg. Chem. 1964, 3, 1794;
    • 3]: T. A. Manuel, Inorg. Chem. 1964, 3, 1794;
  • 22
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    • 2], dmpe = 1,2-bis(dimethylphosphano)ethane: C. A. Tolman, S. D. Ittel, A. D. English, J. P. Jesson, J. Am. Chem. Soc. 1978, 100, 4080;
    • 2], dmpe = 1,2-bis(dimethylphosphano)ethane: C. A. Tolman, S. D. Ittel, A. D. English, J. P. Jesson, J. Am. Chem. Soc. 1978, 100, 4080;
  • 23
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    • 6] (X-ray): M. J. Begley, S. G. Puntambekar, A. H. Wright, J. Chem. Soc. Chem. Commun. 1987, 1251;
    • 6] (X-ray): M. J. Begley, S. G. Puntambekar, A. H. Wright, J. Chem. Soc. Chem. Commun. 1987, 1251;
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    • 3] (X-ray): H. Schäufele, D. Hu, H. Pritzkow, U. Zenneck, Organometallics 1989, 8, 396;
    • 3] (X-ray): H. Schäufele, D. Hu, H. Pritzkow, U. Zenneck, Organometallics 1989, 8, 396;
  • 25
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    • 6)] (X-ray): C. Brodt, S. Niu, H. Pritzkow, M. Stephan, U. Zenneck, J. Organometal. Chem. 1993, 459, 283.
    • 6)] (X-ray): C. Brodt, S. Niu, H. Pritzkow, M. Stephan, U. Zenneck, J. Organometal. Chem. 1993, 459, 283.
  • 26
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    • 8)(dcpe)], dcpe = 1,2-bis(dicyclohexylphosphano)ethane (X-ray): H. Kubo, M. Hirano, S. Komiya, J. Organomet. Chem. 1998, 556, 89.
    • 8)(dcpe)], dcpe = 1,2-bis(dicyclohexylphosphano)ethane (X-ray): H. Kubo, M. Hirano, S. Komiya, J. Organomet. Chem. 1998, 556, 89.
  • 27
    • 33646457204 scopus 로고    scopus 로고
    • 3167; see Table 2
    • J. E. Ellis, Inorg. Chem. 2006, 45, 3167; see Table 2.
    • (2006) Inorg. Chem , vol.45
    • Ellis, J.E.1
  • 28
    • 34548139345 scopus 로고    scopus 로고
    • 2 by alkali-metal naphthalenes provided deep red solutions of presently unknown products. W. W. Brennessel, J. E. Ellis, unpublished results.
    • 2 by alkali-metal naphthalenes provided deep red solutions of presently unknown products. W. W. Brennessel, J. E. Ellis, unpublished results.
  • 29
    • 0004233970 scopus 로고    scopus 로고
    • 3rd ed, Wiley-VCH, Weinheim
    • C. Elschenbroich, Organometallics, 3rd ed., Wiley-VCH, Weinheim, 2006, p. 491.
    • (2006) Organometallics , pp. 491
    • Elschenbroich, C.1
  • 30
    • 34548134213 scopus 로고    scopus 로고
    • Interatomic data for anion 1b have slightly smaller uncertainties (esd's) than those for 1a, so only the former will be discussed in this article, as anion 1.
    • Interatomic data for anion 1b have slightly smaller uncertainties (esd's) than those for 1a, so only the former will be discussed in this article, as anion 1.
  • 31
    • 34548142200 scopus 로고    scopus 로고
    • 2;
    • 2;
  • 32
    • 34548139346 scopus 로고    scopus 로고
    • 2;
    • 2;
  • 33
    • 34548125740 scopus 로고    scopus 로고
    • CCDC-637186 (1a), CCDC-637187 (1b), CCDC-637188 (4), CCDC-637189 (5), and CCDC-637190 (6) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
    • c) CCDC-637186 (1a), CCDC-637187 (1b), CCDC-637188 (4), CCDC-637189 (5), and CCDC-637190 (6) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
  • 34
    • 34548131610 scopus 로고    scopus 로고
    • Coordination geometry is determined by a twist angle, θ, corresponding to the intersection of planes defined by the midpoints of the outer C-C bonds of the coordinated dienes and the iron center. For 1, θ = 85°, compared to 90° for a tetrahedral geometry. In the case of the cod complex 5, the midpoints of the olefinic C-C bonds were used in the calculation of θ.
    • Coordination geometry is determined by a twist angle, θ, corresponding to the intersection of planes defined by the midpoints of the outer C-C bonds of the coordinated dienes and the iron center. For 1, θ = 85°, compared to 90° for a tetrahedral geometry. In the case of the cod complex 5, the midpoints of the olefinic C-C bonds were used in the calculation of θ.
  • 35
    • 34548134063 scopus 로고    scopus 로고
    • Average outer C1-C2 and inner C2-C3 bond lengths in 1 are 1.417(5) and 1.407(4, whereas corresponding values in 2 are 1.416(8) and 1.420(6, A definite, though weak, long-short-long pattern in the coordinated diene C-C bond lengths of 1, but not 2, suggests that Fe -1 may back-bond to anthracene slightly better than Co-1 does in these compounds. However, the metal-carbon bond lengths in 1 and 2 do not support this view and are statistically identical. Thus, the average M-C1,C4 and M-C2,C3 bond lengths in 1 (M, Fe) are 2.14(1) and 2.02(1) Å, respectively, and corresponding values in 2 (M, Co) are 2.13(1) and 1.99(2) Å, where the difference in atomic radii of iron and cobalt is only about 0.01 Å. See: J. Emsley, The Elements, 3rd edition, Oxford, New York, 1998, pp. 60, 106. Also, the average fold angles for coordinated anthracenes in 1 and 2 are 24 and 28°
    • -1 does in these compounds. However, the metal-carbon bond lengths in 1 and 2 do not support this view and are statistically identical. Thus, the average M-C1,C4 and M-C2,C3 bond lengths in 1 (M = Fe) are 2.14(1) and 2.02(1) Å, respectively, and corresponding values in 2 (M = Co) are 2.13(1) and 1.99(2) Å, where the difference in atomic radii of iron and cobalt is only about 0.01 Å. See: J. Emsley, The Elements, 3rd edition, Oxford, New York, 1998, pp. 60, 106. Also, the average fold angles for coordinated anthracenes in 1 and 2 are 24 and 28°, respectively.
  • 47
    • 34548131603 scopus 로고    scopus 로고
    • 2. See reference [14] for CCDC number and related information.
    • 2. See reference [14] for CCDC number and related information.
  • 48
    • 34548136559 scopus 로고    scopus 로고
    • For example, the average outer and inner Fe-C distances in 4, 2.08(2) and 2.02(2, respectively, are essentially identical to corresponding values observed for the 18-electron Fe0 complex [Fe(η 4-C4H6)2(PMe3, 2.084(4) and 2.021(4) Å, 22a] Outer Fe-C distances in substituted {Fe(η4-1,3-diene, complexes tend to be longer, presumably because of steric effects.[22b] Thus, the average outer Fe-C distance in 1 is 2.14(1) Å, whereas respective average inner Fe-C and coordinated diene C-C distances in 1 and 4 are nearly the same
    • [22b] Thus, the average outer Fe-C distance in 1 is 2.14(1) Å, whereas respective average inner Fe-C and coordinated diene C-C distances in 1 and 4 are nearly the same.
  • 51
    • 34548125742 scopus 로고    scopus 로고
    • [18d, 24]
    • [18d, 24]
  • 53
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    • [21]
    • [21]
  • 58
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    • Several neutral 17-electron organoiron(I) complexes have been reported. See: K. Jonas, P. Klusmann, R. Goddard, Z. Naturforsch. B 1995, 50, 394.
    • Several neutral 17-electron organoiron(I) complexes have been reported. See: K. Jonas, P. Klusmann, R. Goddard, Z. Naturforsch. B 1995, 50, 394.
  • 59
    • 34548131605 scopus 로고    scopus 로고
    • Crystal structure determinations were carried out for both salts, 5a and 5b, and confirmed the presence of identical anions. However, the [K([2.2.2]cryptand, structure solution is of higher quality and will be reported herein. Crystal data for 5b: C 40H58FeKN2O6, Mr, 757.83, triclinic, space group P1, iridescent red-violet plate, a, 12.132(5, b, 13.171(6, c, 14.490(7) Å, α, 108.412(7, β, 107.101(7, γ, 107.176(7)°, V, 1897.5(15) Å3, Z, 2, T, 173(2) K, λ, 0.71073 Å, 18644 reflections, 6696 independent, R1, 0.0377 (I > 2σ(I, wR2, 0.0779 (all data, μ, 0.555 mm-1 SADABS, full-matrix least-squares refinement on F 2. See reference [14] for CCDC number and related information
    • 2. See reference [14] for CCDC number and related information.
  • 60
    • 34548128801 scopus 로고    scopus 로고
    • 4- polyarene group in 5 are 2.16(2) and 2.08(1) Å, respectively, and the corresponding values for the cobaltate are 2.15(1) and 2.010(2) Å. The average outer C1-C2 and inner C2-C3 bond lengths in 5 are 1.422(3) and 1.401(4), whereas corresponding values for the cobaltate are 1.419(5) and 1.400(2) Å, respectively. Average M-C bond lengths for the cod groups in 5 and the cobaltate are 2.05(1) and 2.019(8) Å, respectively, whereas corresponding average olefinic C-C bond lengths are 1.416(4) and 1.406(6) Å.
    • 4- polyarene group in 5 are 2.16(2) and 2.08(1) Å, respectively, and the corresponding values for the cobaltate are 2.15(1) and 2.010(2) Å. The average outer C1-C2 and inner C2-C3 bond lengths in 5 are 1.422(3) and 1.401(4), whereas corresponding values for the cobaltate are 1.419(5) and 1.400(2) Å, respectively. Average M-C bond lengths for the cod groups in 5 and the cobaltate are 2.05(1) and 2.019(8) Å, respectively, whereas corresponding average olefinic C-C bond lengths are 1.416(4) and 1.406(6) Å.
  • 63
    • 34548134061 scopus 로고    scopus 로고
    • 2. See reference [14] for CCDC number and related information.
    • 2. See reference [14] for CCDC number and related information.
  • 64
    • 34548134062 scopus 로고    scopus 로고
    • [9d]
    • [9d]
  • 67
    • 34548119116 scopus 로고    scopus 로고
    • This observation is consistent with an analysis of loss of resonance energies (ΔRE) that occur when arenes bind to a given metal, oxidation state, and ligand set.[2c] On this basis, the {M(η4- arene, bond energy will increase in the order naphthalene < anthracene. However, the corresponding {Mη6-arene, bond energy will increase in the opposite order, that is, anthracene < naphthalene. This simple analysis does not include steric effects or intrinsic differences in the donor and acceptor abilities of the bound arenes. A recent study by Parkin and co-workers also considers these issues.[2c
    • [2c]
  • 71
    • 33751224183 scopus 로고    scopus 로고
    • M. P. Hendrich, W. Gunderson, R. K. Behan, M. T. Green, M. P. Mehn, T. A. Betley, C. C. Lu, J. C. Peters, Proc. Natl. Acad. Sci. USA 2006, 103, 17107, and references therein.
    • c) M. P. Hendrich, W. Gunderson, R. K. Behan, M. T. Green, M. P. Mehn, T. A. Betley, C. C. Lu, J. C. Peters, Proc. Natl. Acad. Sci. USA 2006, 103, 17107, and references therein.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.