Stereoelectronic effects in dihapto-coordinated complexes of TpW (NO)(PMe 3) and their manifestation in diels - Alder cycloaddition of arenes

Organometallics

Volumn 28, Issue 16, 2009, Pages 4724-4734

  Salomon, Rebecca J ^a   Lis Jr , Edward C ^a   Kasbekar, Monica U ^a   Bassett, Kimberley C ^a   Myers, William H ^b   Trindle, Carl O ^a   Sabat, Michal ^a   Harman, W Dean ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

^b UNIVERSITY OF RICHMOND   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COORDINATED COMPLEXES; CYCLOADDITION TRANSITION; DFT CALCULATION; DIASTEREOMERS; DIELS-ALDER CYCLOADDITIONS; DIENOPHILES; DIMETHOXYBENZENE; FASTER REACTIONS; FUNCTIONALIZED; METAL FRAGMENTS; METHOXY; POSITIVE CHARGES; STEREOELECTRONIC EFFECT; SYNTHETIC APPLICATION;

LIGANDS; OLEFINS; SULFUR COMPOUNDS;

REACTION RATES;

EID: 68949177301     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om900381c     Document Type: Article

References (24)

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9. endo and exo refer to stereochemistry of dienophile addition relative to the uncoordinated diene fragment of the arene. Thus, the endo isomer of 2 has the succinimide ring extending away from the metal.
10. Eliel, E. L.; Wilen, S. H.; Mander, L. N. Sterochemistry of Organic Compounds; J. Wiley & Sons, Inc.; New York, 1994.
11. The term coordination diastereomers refers herin to two isomers differing in stereochemistry resulting from coordination to the metal.
12. For fumaronitrile, exo refers to the nitrile group alpha to the bridgehead methoxy substituent. A trans stereochemistry is maintained for the two cyano groups in all cycloadducts.
13. Graham, P. M.; Delafuente, D. A.; Liu, W.; Myers, W. H.; Sabat, M.; Harman, W. D. J. Am. Chem. Soc. 2005, 127, 10568.
14. Hannan, W. D. Coord. Chem. Rev. 2004, 853.
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18. Lis, E. C.; Delafuente, D. A.; Lin, Y.; Mocella, C. J.; Todd, M. A.; Liu, W.; Sabat, M.; Myers, W. H.; Harman, W. D. Organometallics 2006, 25, 5051.
19. DFT calculations for the related system TpRc(CO)(McIm)-(naphthalenium) indicate two conformational energy minima for this type of asymmetric allvl species. See: Lis, E. C.; Delafuente, D. A.; Lin, Y.; Mocella, C. J.; Todd, M. A.; Liu, W.; Sabat, M.; Myers, W. H.; Harman, W. D. Organometllics 2006, 25, 5051.
20. Mocclla, C. J.; Delafuente, D. A.; Keane, J. M.; Warner, G. R.; Friedman, L. A.; Sabat, M.; Harman, W. D. Organometallics 2004, 23, 3772.
21. This was first briefly noted in ref 11.
22. Here GAUSSIAN03W rev D has computed the charge distribution from a LSDA/LANL2DZ wave function: the density isosurfaee, displayed by GAUSSVIEW 3.09, is 0.0004 electron per cubic Bohr, and the electrostatic potential is evaluated only on that surface. The color coding defines red as the most negative potential (stabilizing to a positive test charge). Only the O atom of NO is so extreme on the molecular periphery. Blue is most positive; intermediate values follow the spectral order; that is, green represents a less positive potential relative to blue. That is, the trirnethylphosphine fragment at top is more positive than the scorpionate zone at bottom. The range of potentials is roughly 0.065 atomic unit (hartrees per electron).
23. Bassett, K. C.; You, F.; Graham, P. M.; Myers, W. H.; Sabat, M.; Harman, W. D. Organometallics 2005, 25, 435.
24. Welch, K. D.; Smith, P. L.; Keller, A. P.; Myers, W. H.; Sabat, M.; Harman, W. D. Organometallics 2006, 25, 5067.