How a bidentate ligand may favor the unusual cis isomer in dioxo d2 octahedral transition metal complexes: An EHMO study

New Journal of Chemistry

Volumn 20, Issue 1, 1996, Pages 53-63

  Demachy, Isabelle ^a   Jean, Yves ^a  

^a UNIVERSITÉ PARIS SUD   (France)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0042290479     PISSN: 11440546     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article

References (41)

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2. See also: b) Burdett J. K., Structure and Bonding, 1987, 65, 29;
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4. 2 dioxo complexes, see d) Veldkamp A., Frenking G., J. Am. Chem. Soc., 1994, 116, 4937.
5. 0 dioxo complexes, see: e) Brower D. C., Templeton J. L., Mingos D. M. P., J. Am. Chem. Soc., 1987, 109, 5203;
6. f) Tatsumi K., Hoffmann R., Inorg. Chem., 1980, 19, 2656.
7. For an experimental review, see g) Holm R. H., Chem. Rev., 1987, 87, 1401;
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10. b) Dovletoglou A., Meyer T. J., J. Am. Chem. Soc., 1994, 116, 215 and references therein.
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12. b) Li C-K., Che C-M., Tong W.-F., Tang W.-T., Wong K.-Y., Lai T.-F., J. Chem. Soc., Dalton Trans., 1992, 2109.
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15. Blackbourn R. L., Jones L. M., Ram M. S., Sabat M., Hupp J. T., Inorg. Chem., 1990, 29, 1791. For this complex, the formation of the cis isomer might reflect a kinetic preference, but the expected trans isomer is still unknown.
16. Perrier S., Lau T. C., Kochi J. K., Inorg. Chem., 1990, 29, 4190.
17. a) Johnson J. W., Brody J. F., Ansell G. B., Zentz S., Inorg. Chem., 1984, 23, 2415;
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23. Demachy I., Jean Y., New J. Chem., 1995, 19, 763.
24. ij formula is used: Ammeter J. H., Bürgi H.-B., Thibeault J. C., Hoffmann R., J. Am. Chem. Soc., 1979, 101, 3141.
25. References for atomic basis sets: a) Re: Shaik S., Hoffmann R., Fisel C. R., Summerville R. H., J. Am. Chem. Soc., 1980, 102, 4555;
26. b) Os: Evans D., Mingos D. M. P., Organometallics, 1983, 2, 435;
27. c) Cl, C, N, O, H: Albright T. A., Hoffmann R., Thibeault J. C., Thorn D. L., J. Am. Chem. Soc., 1979, 101, 3801;
28. d) Ru: Tuan D. F.-T., Hoffmann R., Inorg. Chem., 1985, 24, 871.
29. a) Kruse F. H., Acta Cryst., 1961, 14, 1035;
30. b) Day V. W., Hoard J. L., J. Am. Chem. Soc., 1968, 90, 3374;
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33. e) Perrier S., Kochi J. K., Inorg. Chem., 1988, 27, 4165.
34. Loza M. L., de Gala S. R., Crabtree R. H., Inorg. Chem., 1994, 33, 5073.
35. 2a (X-ray structure still unknown).
36. This method has previously been used with success to trace a link between the geometry of a complex and the σ donor or acceptor properties of some ligands. See, for instance: Tatsumi K., Hoffmann R., Yamamoto A., Stille J. K., Bull. Chem. Soc. Jpn, 1981, 54, 1857.
37. Demachy I., Jean Y., to be submitted.
38. CH2 orbitals carried by the vicinal methylene groups, leading to a butadiene-like π system with the four π orbitals doubly occupied. Taking into account these four orbitals (instead of two) does not change the conclusions, the number of stabilizing (or destabilizing) interactions being simply multiplied by two.
39. This conclusion is in agreement with the comment given in footnote 18 of ref. 6.
40. a) Patton A. T., Strouse C. E., Knobler C. B., Gladysz J. A., J. Am. Chem. Soc., 1983, 105, 5804;
41. b) Miessler G. L., Kim S., Jacobson R. A., Angelici R. J., Inorg. Chem., 1987, 26, 1690.