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Volumn 25, Issue 9, 2006, Pages 2173-2181

Computational studies of structures and properties of metallaboranes. 2. Transition-metal dicarbollide complexes

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEXATION; NUCLEAR MAGNETIC RESONANCE; ORGANOMETALLICS; PROBABILITY DENSITY FUNCTION; TRANSITION METALS;

EID: 33646450411     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om051025f     Document Type: Article
Times cited : (45)

References (111)
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    • (b) Review: Bühl, M. In Encyclopedia of Computational Chemistry; Schleyer, P. v. R., Allinger, N. L., Kollman, P. A., Clark, T., Schaefer, H. F., Gasteiger, J., Schreiner, P. R., Eds.; Wiley: Chichester, 1998; p 1835.
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    • See for instance: (a) Koch, W.; Holthausen, M. C. A Chemist's Guide to Density Functional Theory; Wiley-VCH: Weinheim, 2000, and the extensive bibliography therein. It should be noted that hybrid functionals such as B3LYP need not be superior to pure, gradient-corrected functionals, as far as geometries of transition-metal complexes are concerned.
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    • Koch, W.1    Holthausen, M.C.2
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    • note
    • -).
  • 63
    • 0034602077 scopus 로고    scopus 로고
    • Selected examples for Co: (b) QAJNAQ (ref-code in Cambridge Structure Database): Hardie, M. J.; Raston, C. L. Angew. Chem., Int. Ed. 2000, 39, 3835.
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    • For a derivative bearing a metal-complexed indenyl substituent on one of the dicarbollides see: HAFDEX: Lewis, Z. G.; Welch, A. J. J. Organomet. Chem. 1992, 438, 353.
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    • note
    • It should be noted that the experimental numbers may be noticeably affected by packing effects, since for instance for the Co anion, where numerous X-ray crystal structures with different counterions and cocrystallized molecules are known, the respective distances can vary substantially from one crystal to the other, or from one dicarbollide unit to the other in case both are not equivalent due to a lower symmetry in the crystal.
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    • 11)] it has recently been suggested that the parent cobalt bis(dicarbollide) 1 should prefer a cisoid arrangement (Viñas, C.; Llop J.; Teixidor, F.; Kivekäs R, Sillanpää, R. Chem. Eur. J. 2005, 11, 1933), a notion that is not supported by our results.
    • (2005) Chem. Eur. J. , vol.11 , pp. 1933
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    • note
    • The MO corresponding to that shown for 1(180°) is lower in energy in 3(180°), where it appears as HOMO-3.
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    • note
    • The second-highest from the barriers in Table 2.
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    • (b) Refcode MEFNEQ in the Cambridge Structure Database, cited as: Ellis, D.; Jellis, P.; Stone, F. G. Private communication, 2000.
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    • and references therein
    • The large downfield shift of the remote (antipodal) B(10) resonance on going from 8 to 9 is noteworthy. Apparently, the increased π-back-bonding from the metal to the CO ligands as compared to benzene makes the whole metal fragment more electronegative; similar remote shifts produced by electronegative elements in borane cages are well known as the "antipodal effect", cf.: Bühl, M.; Schleyer, P. v. R.; Havlas, Z.; Hnyk, D.; Hermanek, S. Inorg. Chem. 1991, 30, 3107, and references therein.
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    • note
    • It should be recalled at this point that at the simplest conventional ab initio level, Hartree-Fock, very poor chemical shifts are obtained for 1, cf. ref 10.
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    • The so-called Malkin correction (in an SOS-DFPT scheme), which is beneficial for many main-group compounds, is indicated to affect ligand shifts only marginally, cf.: (c) Wilson, P. J.; Amos, R. D.; Handy, N. C. Phys. Chem. Chem. Phys. 2000, 2, 187.
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    • note
    • +, respectively (taken from ref 52).
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    • note
    • It should be noted that these formal charges do not reflect the actual electron distribution; for example, for the Ni atom in 3(36°) an NPA charge of +0.67 is obtained at the B3LYP/II' level, much smaller than the formal value, +4.
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    • For selected reviews see: (a) Kaupp, M.; Malkin, V. G.; Malkina, O. L. In The Encyclopedia of Computational Chemistry; Schleyer, P. v. R., Allinger, N. L., Clark, T., Gasteiger, J., Kollman, P. A., Schaefer, H. F., III; Schreiner, P. R., Eds.; Wiley: Chichester, 1998; p 1857.
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    • Reference 29b
    • (c) Reference 29b.
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    • note
    • According to natural bond orbital analysis (ref 23), the (multicenter) bonds between Ru and the carborane moiety are characterized by essentially pure d-orbital contributions from the metal, with little or no s-character. Thus, an efficient Fermi-contact interaction between Ru and adjacent B atoms is precluded, which would be the principal mechanism for the transfer of SO effects on nuclear shieldings, cf. ref 64.
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    • note
    • Incidentally, of the possible forms 13a-c considerd, the 2,10-isomer 13c is also the most stable one thermodynamically, 12.8 and 74.3 kJ/mol below 13b and 13a, respectively.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.