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Volumn 46, Issue 26, 2007, Pages 11277-11290

Substituent effects in formally quintuple-bonded ArCrCrAr compounds (Ar = terphenyl) and related species

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EID: 38149082806     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic702112e     Document Type: Article
Times cited : (130)

References (81)
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    • Sheldrick, G. M. (personal communication) TWINABS: An Empirical Correction for Absorption Anisotropy applied to Twinned crystals, version 1.05; Universität Göttingen: Göttingen, Germany, 2003.
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    • 2 was also entertained. This cannot be excluded on the basis of the Cr-X distances (X = O vs F); however, replacing the bridging F atoms with O led to a significantly worse final refinement of the crystal structure. Furthermore, no O-H stretch was observed in the IR spectrum of 5, and the synthesis was reproducible when air and moisture were carefully excluded.
    • 2 was also entertained. This cannot be excluded on the basis of the Cr-X distances (X = O vs F); however, replacing the bridging F atoms with O led to a significantly worse final refinement of the crystal structure. Furthermore, no O-H stretch was observed in the IR spectrum of 5, and the synthesis was reproducible when air and moisture were carefully excluded.
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    • The formal bond order is assigned on the basis that five singly occupied Orbitals from each Cr participate in the bonding. However, the effective bond order is smaller than 5 because of the interaction of metal-metal bonding and antibonding orbitale and has been calculated to be 3.52 for the model complex PhCrCrPh at the CASSPT2 level of theory.
    • The formal bond order is assigned on the basis that five singly occupied Orbitals from each Cr participate in the bonding. However, the effective bond order is smaller than 5 because of the interaction of metal-metal bonding and antibonding orbitale and has been calculated to be 3.52 for the model complex PhCrCrPh at the CASSPT2 level of theory.
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    • Note that the C(ortho)-C(ipso)-Cr angles are very similar, but not identical, in the optimized PhCrCrPh model; such an effect could be associated with an agostic Cr-H interaction
    • Note that the C(ortho)-C(ipso)-Cr angles are very similar, but not identical, in the optimized PhCrCrPh model; such an effect could be associated with an agostic Cr-H interaction.
  • 66
    • 38149021020 scopus 로고    scopus 로고
    • Compare the respective values in the crystal structure of 1: C2-C1-Cr1 = 114.34(7)°; C2-C1-Cr1 = 131.74(7)°.
    • Compare the respective values in the crystal structure of 1: C2-C1-Cr1 = 114.34(7)°; C2-C1-Cr1 = 131.74(7)°.
  • 67
    • 38149050941 scopus 로고    scopus 로고
    • iPr group are 2.559-2.797 Å, while the sum of the van der Waals radii of C and H is 3.1 Å. Compare: Wibert, N. Holleman-Wiberg: Lehrbuch der Anorganischen Chemie, 101st ed.; Walter de Gruyter: Berlin, 1995.
    • iPr group are 2.559-2.797 Å, while the sum of the van der Waals radii of C and H is 3.1 Å. Compare: Wibert, N. Holleman-Wiberg: Lehrbuch der Anorganischen Chemie, 101st ed.; Walter de Gruyter: Berlin, 1995.
  • 68
    • 84990128891 scopus 로고    scopus 로고
    • For examples of two-coordinate chromium(II) complexes, see the following, a, Cr(NMes{BMes2})2, Bartlett, R. A, Chen, H, Power, P. P. Angew. Chem, Int. Ed. 1989, 28, 316
    • 2]: Bartlett, R. A.; Chen, H.; Power, P. P. Angew. Chem., Int. Ed. 1989, 28, 316.
  • 69
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    • 2]: Chen, H.; Bartlett, R. A.; Olmstead, M. M.; Power, P. P.; Shoner, S. C. J. Am. Chem. Soc. 1990, 112, 1084.
    • 2]: Chen, H.; Bartlett, R. A.; Olmstead, M. M.; Power, P. P.; Shoner, S. C. J. Am. Chem. Soc. 1990, 112, 1084.
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    • 20644468600 scopus 로고    scopus 로고
    • 2]: Nguyen, T.; Panda, A.; Olmstead, M. M.; Richards, A. F.; Stender, M.; Brynda, M.; Power, P. P. J. Am. Chem. Soc. 2005, 127, 8545.
    • 2]: Nguyen, T.; Panda, A.; Olmstead, M. M.; Richards, A. F.; Stender, M.; Brynda, M.; Power, P. P. J. Am. Chem. Soc. 2005, 127, 8545.
  • 73
    • 38149020280 scopus 로고    scopus 로고
    • The Cr-O distances of 88 Cr-THF complexes in the Cambridge Crystal Structure Database (version 5.27, Aug 2006) range from 1.994 to 2.449 Å, with a median of 2.097 Å.
    • The Cr-O distances of 88 Cr-THF complexes in the Cambridge Crystal Structure Database (version 5.27, Aug 2006) range from 1.994 to 2.449 Å, with a median of 2.097 Å.
  • 74
    • 38149000465 scopus 로고    scopus 로고
    • 3 complexes in the Cambridge Crystal Structure Database (version 5.27, Aug 2006) range from 2.288 to 2.525 Å, with a median of 2.383 Å.
    • 3 complexes in the Cambridge Crystal Structure Database (version 5.27, Aug 2006) range from 2.288 to 2.525 Å, with a median of 2.383 Å.
  • 81
    • 38149050189 scopus 로고    scopus 로고
    • 2 ligand were located on the Fourier difference map and refined freely for both crystallographically independent molecules in the X-ray crystal structure of 8.
    • 2 ligand were located on the Fourier difference map and refined freely for both crystallographically independent molecules in the X-ray crystal structure of 8.


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