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Volumn , Issue 26, 2009, Pages 5077-5082

Intramolecular apical Metal-H-Csp3 interaction in molybdenum and silver complexes

Author keywords

[No Author keywords available]

Indexed keywords

APICAL POSITIONS; COORDINATION MODES; DESHIELDING; FREE LIGANDS; HYDROGEN ATOMS; INPUT PARAMETER; METAL CENTRES; METAL COORDINATION; PHOSPHORUS ATOM; SILVER COMPLEXES; SOLID-STATE STRUCTURES; THEORETICAL CALCULATIONS;

EID: 67649674736     PISSN: 14779226     EISSN: 14779234     Source Type: Journal    
DOI: 10.1039/b823267a     Document Type: Article
Times cited : (14)

References (42)
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    • 0 complexes. In this case the local Lewis acidity at the metal centre controls these interactions (ref. 7). By contrast, in the case of late-transition complexes M←HC electron donation appears to play a significant role, and shows characteristic features, such as elongated C-H bonds
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    • (1983) J. Organomet. Chem. , vol.250 , pp. 395
    • Brookhart, M.1    Green, M.L.H.2
  • 8
    • 3142663134 scopus 로고    scopus 로고
    • 10 metal centres in M-HX systems (X = N, O, S). However, the bonding situation in the M-H-C has been a matter of debate. Some authors consider more appropriate the term "anagostic" to describe M-H-C interactions that do not involve 3c-2e interactions. See ref. 2, ref. 3, and:
    • W. Scherer G. S. McGrady Angew. Chem. Int. Ed. 2004 43 1782
    • (2004) Angew. Chem. Int. Ed. , vol.43 , pp. 1782
    • Scherer, W.1    McGrady, G.S.2
  • 24
    • 33845469247 scopus 로고
    • All the molecular systems were optimized from X-ray diffraction data. DFT-B3PW91 and two layer basis sets (Intern layer: All atoms 6-31g(d) and M LANL2DZ, Outer layer C, H 3-21g) approach methodology to model the complexes have been used. Stationary points were characterized by frequency analysis. All the calculations, including, GIAO and orbital analysis (NBO 3.0), have been carried out Gaussian 03 program package. A detailed description of the methods is provided in the ESI.
    • F. Cecconi C. A. Ghilardi P. Innocenti C. Mealli S. Midollini A. Orlandini Inorg. Chem. 1984 23 922
    • (1984) Inorg. Chem. , vol.23 , pp. 922
    • Cecconi, F.1    Ghilardi, C.A.2    Innocenti, P.3    Mealli, C.4    Midollini, S.5    Orlandini, A.6
  • 26
    • 77956718184 scopus 로고
    • Additionally, natural population analysis points in the same direction than NBO analysis (Ag: 0.205 e, Mo: 0.039 e), and bond order calculations agrees with a CH-M interaction (Wiber bond index matrix in the natural atomic orbitals (NAO), atom-atom overlap-weighted NAO bond order, and MO bond order are 0.06, 0.09 and 0.19 (Ag-HC), and 0.04, 0.08, and 0.16 (Mo-HC). See ref. 22
    • R. H. Crabtree D. G. Hamilton Adv. Organomet. Chem. 1988 28 299
    • (1988) Adv. Organomet. Chem. , vol.28 , pp. 299
    • Crabtree, R.H.1    Hamilton, D.G.2
  • 27
    • 0011083499 scopus 로고
    • C-H to metal delocalization energies goes up to as much as 57 kcal/mol for strongly agostic interactions, see ref. 8 and
    • A. E. Reed L. A. Curtiss F. Weinhold Chem. Rev. 1988 88 899
    • (1988) Chem. Rev. , vol.88 , pp. 899
    • Reed, A.E.1    Curtiss, L.A.2    Weinhold, F.3
  • 34
    • 84985611078 scopus 로고
    • Abramov has proposed an approximation to compute G(r) from the experimental electron density ρ(r). This approach allows a quantitative and semi-quantitative description of the G(r) behaviour at the BCPs of compounds with closed-shell and shared interactions, respectively. See:
    • D. Cremer E. Kraka Angew. Chem. Int. Ed. 1984 23 627
    • (1984) Angew. Chem. Int. Ed. , vol.23 , pp. 627
    • Cremer, D.1    Kraka, E.2
  • 39
    • 0034669695 scopus 로고    scopus 로고
    • There is some controversial at this point. It has been reported that a very small critical bond could be not an indication of a genuine weak bond (see ref. 30). Our values are in good agreement with those recently reported for weak interactions (see ref. 31)
    • I. Rozas I. Alkorta J. Elguero J. Am. Chem. Soc. 2000 122 11154
    • (2000) J. Am. Chem. Soc. , vol.122 , pp. 11154
    • Rozas, I.1    Alkorta, I.2    Elguero, J.3
  • 42
    • 0004150157 scopus 로고    scopus 로고
    • Bruker AXS, Inc. Madison, Wisconsin, USA
    • G. M. Sheldrick, SHELXTL 6.1, Bruker AXS, Inc. Madison, Wisconsin, USA, 2001
    • (2001) SHELXTL 6.1
    • Sheldrick, G.M.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.