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Volumn 119, Issue 52, 1997, Pages 12800-12814

Monomeric cyclopentadienylnickel methoxo and amido complexes: Synthesis, characterization, reactivity, and use for exploring the relationship between H-X and M-X bond energies

Author keywords

[No Author keywords available]

Indexed keywords

AMIDE; METAL COMPLEX; NICKEL COMPLEX; OXIDE;

EID: 0031593030     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja971829p     Document Type: Article
Times cited : (133)

References (127)
  • 3
    • 0011509370 scopus 로고    scopus 로고
    • and other articles in the same issue
    • For leading references, see: Holm, R. H.; Kennepohl, P.; Solomon, E. I. Chem. Rev. 1996, 96, 2239, and other articles in the same issue.
    • (1996) Chem. Rev. , vol.96 , pp. 2239
    • Holm, R.H.1    Kennepohl, P.2    Solomon, E.I.3
  • 23
    • 2642619351 scopus 로고
    • n-Cyclopentadienyl Complexes
    • Wilkinson, G., Ed.; Pergamon: New York
    • Jolly, P. W. n-Cyclopentadienyl Complexes. In Comprehensive Organometallic Chemistry, 1st ed.; Wilkinson, G., Ed.; Pergamon: New York, 1982; Vol. 6, p 189.
    • (1982) Comprehensive Organometallic Chemistry, 1st Ed. , vol.6 , pp. 189
    • Jolly, P.W.1
  • 30
    • 2642651064 scopus 로고    scopus 로고
    • note
    • Presumably, the problems with methanol addition lie in the difficulty of completely freeing methanol from trace water.
  • 36
    • 0001319291 scopus 로고
    • 3-Benzyl complexes of nickel are known: Cámpora, J.; Gutiérrez, E.; Poveda, M. L.; Ruiz, C.; Carmona, E. J. Chem. Soc., Dalton Trans. 1992, 1769. Carmona, E.; Paneque, M.; Poveda, M. L. Polyhedron 1989, 8, 285.
    • (1989) Polyhedron , vol.8 , pp. 285
    • Carmona, E.1    Paneque, M.2    Poveda, M.L.3
  • 54
    • 0030899136 scopus 로고    scopus 로고
    • β-Hydrogen elimination can proceed through other pathways in coordinatively saturated complexes. See: Ritter, J. C. M.; Bergman, R. G. J. Am. Chem. Soc. 1997, 119, 2580.
    • (1997) J. Am. Chem. Soc. , vol.119 , pp. 2580
    • Ritter, J.C.M.1    Bergman, R.G.2
  • 71
    • 0000954004 scopus 로고
    • An outer-sphere phenolate has been observed in a ruthenium complex but this was aided by extensive hydrogen bonding to excess phenol. Burn, M. J.; Fickes, M. G.; Hollander, F. J.; Bergman, R. G. Organametallics 1995, 14, 137.
    • (1995) Organametallics , vol.14 , pp. 137
    • Burn, M.J.1    Fickes, M.G.2    Hollander, F.J.3    Bergman, R.G.4
  • 72
    • 2642611892 scopus 로고    scopus 로고
    • note
    • Unfortunately, we have not been able to isolate pure samples of ethyltetramethylcyclopentadienyl analogues of the nickel amido complexes in order to perform crossover experiments here.
  • 75
    • 0000829601 scopus 로고
    • Ru-P), with N and O ligands giving the weakest Ru-P bond and C and H ligands giving the strongest Ru-P bond. In the system described here, the Ni-P bond lengths imply a similar trend (see ref 22). However, their phosphine dissociation was aided by π-bonding in the unsaturated intermediate; no such mechanism is possible for me complexes here (see ref 7). Since we have no way to accurately evaluate the Ni-P bond strengths, this effect is ignored here. Note that this does not invalidate our estimates of bond energy differences, because bond energies are defined to include changes in ancillary bonding (see footnote 34 in ref 87).
    • (1989) Organometallics , vol.8 , pp. 379
    • Bryndza, H.E.1    Domaille, P.J.2    Paciello, R.A.3    Bercaw, J.E.4
  • 76
    • 85045499329 scopus 로고    scopus 로고
    • Entropic factors in our system will be discussed more thoroughly below
    • Since translational entropy is conserved. AS should be small in systems in which two particles are converted into two particles. See: Minas de Piedade, M. E.; Simões, J. A. M. J. Organomet. Chem. 1996, 518, 167. Entropic factors in our system will be discussed more thoroughly below.
    • (1996) J. Organomet. Chem. , vol.518 , pp. 167
    • De Minas Piedade, M.E.1    Simões, J.A.M.2
  • 77
    • 2642639574 scopus 로고    scopus 로고
    • note
    • 2) was shown to be largely due to a steric (entropic) effect. Large deviations were also observed for X ligands that bind through a second-row atom or can participate in backbonding.
  • 78
    • 2642709150 scopus 로고    scopus 로고
    • note
    • nM and R (and, fortuitously, H-X BDE) held constant, the oxygen ligand binds more strongly than the nitrogen ligand.
  • 79
    • 2642712436 scopus 로고    scopus 로고
    • note
    • In this kind of graph, deviations from 1:1 behavior are dampened by the fact that both axes contain BDE(H-X). Thus, a systematic deviation from 1:1 behavior (such as that in ref 81) can appear to give a H-X/M-X graph with a slope nearly equal to 1.0.
  • 80
    • 2642708306 scopus 로고    scopus 로고
    • note
    • p(Ac). Thus, the deprotonation of benzoic acids is a poorer model for Ni-N/H-N exchange, as are other Hammett substituent constants.
  • 91
    • 0345211121 scopus 로고
    • A reviewer has pointed out that these bond energies are undoubtedly affected by constructive π-interaction between M and X
    • Schock, L. E.; Marks, T. J. J. Am. Chem. Soc. 1988, 110, 7701. A reviewer has pointed out that these bond energies are undoubtedly affected by constructive π-interaction between M and X.
    • (1988) J. Am. Chem. Soc. , vol.110 , pp. 7701
    • Schock, L.E.1    Marks, T.J.2
  • 92
    • 0000537546 scopus 로고
    • Although absolute bond energies derived from calculations are usually not highly accurate, differences in bond energies are more trustworthy
    • Ziegler, T.; Tschinke, V.; Versluis, L.; Baerends, E. J.; Ravenek, W. Polyhedron 1988, 7, 1625. Although absolute bond energies derived from calculations are usually not highly accurate, differences in bond energies are more trustworthy.
    • (1988) Polyhedron , vol.7 , pp. 1625
    • Ziegler, T.1    Tschinke, V.2    Versluis, L.3    Baerends, E.J.4    Ravenek, W.5
  • 100
    • 2642648586 scopus 로고    scopus 로고
    • note
    • E = +0.10).
  • 103
    • 2642609418 scopus 로고    scopus 로고
    • note
    • 5-Cp rings) leads us to believe that a simple associative mechanism is quite reasonable, the 18-electron "rule" (for which there are many exceptions) notwithstanding.
  • 105
    • 2642672757 scopus 로고    scopus 로고
    • note
    • See ref 96. We hope that others will carry out quantitative E-C analyses that test the generality of the notions presented here. Such studies should be performed on more robust systems than these nickel complexes, so that entropy changes can be evaluated, and so that decomposition does not limit the choice of ligands.
  • 122
    • 2642614470 scopus 로고    scopus 로고
    • note
    • Although the absolute temperature is not known to an accuracy of better than ±3 K, the temperature was maintained to ±0.1 K within each kinetic run using 4.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.