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Volumn 120, Issue 15, 1998, Pages 3762-3772

On the nature and incidence of β-agostic interactions in ethyl derivatives of early transition metals: Ethyltitanium trichloride and related compounds

Author keywords

[No Author keywords available]

Indexed keywords

COORDINATION COMPOUND; ETHYLENE DERIVATIVE; METAL DERIVATIVE; TITANIUM DERIVATIVE;

EID: 0032557208     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9737578     Document Type: Article
Times cited : (78)

References (75)
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    • Statistical analysis of the C-C bond distances in transition metal ethyl compounds based on 107 X-ray structures in the Cambridge Structural Database 5.10 (ref 7a) yields an average of 147.5 pm. These bond distances may, however, suffer from systematic shortening due to polarisation effects.
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    • 2 on the basis of SCF and LDF-DFT calculations. For further information, see: (a) Endo, J.; Koga, N.; Morokuma, K. Organometallics 1993, 12, 2777-2787. (b) Munakata, H.; Ebisawa, Y.; Takashima, Y.; Wrinn, M. C.; Scheiner, A. C.; Newsam, J. M. Catal. Today 1995, 23, 402-408. (c) Koga, N.; Obara, S.; Morokuma, K. J. Am. Chem. Soc. 1984, 106, 4625-4626.
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    • 6 was also underestimated by DFT calculations (62 ppm). For further information see Kaupp, M. J. Am. Chem. Soc. 1996, 118, 3018-3024.
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    • + and report parameters in good agreement with ours: Fan, L.; Harrison, D.; Deng, L.; Woo, T. K.; Swerhone, D.; Ziegler, T. Can. J. Chem. 1995, 73, 989-998. These studies explored neither the potential surface around the equilibrium geometry nor the nature of the bonding therein.
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    • note
    • 2 is extremely flat, and so we should add two cautionary notes. First, even small changes in the computational approach could have a large effect on the optimal value of the TiCC angle. Second, the shape of the barrier to methyl group rotation might be significantly changed, particularlarly in the range from τ = 40 to 60°.
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    • note
    • s model of 7 with the ethyl group locked in the eclipsed conformation and obtained geometric parameters in reasonable agreement with ours; see ref 20a.
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    • note
    • 3 has a very low frequency, however, and it is impossible to exclude the possibility that calculations at a higher level would convert the staggered model to a transition state for methyl group rotation.
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    • Department of Theoretical Chemistry, Vrije Universiteit, de Boelelaan 1083, 1081 HV Amsterdam, Netherlands
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.