X-ray crystal structures of Cp*Ni(PEt3)X [X = Br, O(p-C6H4Me), NH(p- C6H4Me), S(p-C6H4Me), OCH3, CH2C6H5, Me, H, PEt3+]. Understanding distortions and trans influences in cyclopentadienyl complexes

Journal of the American Chemical Society

Volumn 119, Issue 52, 1997, Pages 12815-12823

  Holland, Patrick L ^a   Smith, Michael E ^a   Andersen, Richard A ^a   Bergman, Robert G ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPENTADIENE DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; COMPLEX FORMATION; CRYSTAL STRUCTURE; GEOMETRY; STRUCTURE ANALYSIS; X RAY CRYSTALLOGRAPHY;

EID: 0031593023     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja971830o     Document Type: Article

References (26)

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4. 1H NMR spectroscopy.
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6. Holland, P. L.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1997, 119, 12800. Crystallographic details and an ORTEP diagram of 1-NHTol may be found there.
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11. An ORTEP diagram of 1-H may be found in the Supporting Information.
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15. For a review on "slipped" cyclopentadienyl rings, see: O'Connor, J. M.; Casey, C. P. Chem. Rev. 1987, 87, 307.
16. In a recent paper, these distortions are referred to as "staggered" and "eclipsed", respectively: Cross, R. J.; Hoyle, R. W.; Kennedy, A. R.; Manojlovic-Muir, L.; Muir, K. W. J. Organomet. Chem. 1994, 468, 265. In this paper, a CpPd(X)(L) complex was found to have a distortion of the type we call "intermediate", and this (combined with an analysis of several previously characterized Cp*Pd(X)(L) complexes) led Cross et al. to use many of the same arguments found here. However, we can draw firmer conclusions because (a) the Cp* ligand is less prone to librational motion, and (b) this paper lists a larger range of similar complexes.
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20. s symmetry of Figure 6b (in which σ is horizontal, and the HOMO and LUMO in Figure 7 are a″ and a′, respectively).
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22. This conclusion was also reached by Cross et al. for CpPd(X)(L) complexes. See ref 16.
23. This generalization did not hold for complexes with ligands of indeterminate oxidation level (e.g., catecholate), those with activating or chelating groups on the Cp ring, three-legged piano stools, or polymetallic complexes. This is due to changes in the orbitals at the metal which invalidate the explanation presented above.
24. Holland, P. L., Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1996, 118, 1092.
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