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Volumn 6, Issue 6, 2011, Pages 1423-1430

Alkyne insertion into the M-P and M-H bonds (M=Pd, Ni, Pt, and Rh): A theoretical mechanistic study of the C-P and C-H bond-formation steps

Author keywords

alkyne; catalysis; insertion; selectivity; transition metals

Indexed keywords

ALKYNE; ALKYNE INSERTIONS; HYDROPHOSPHINYLATION; INSERTION; MECHANISTIC STUDIES; METAL HYDROGEN BONDS; METAL-PHOSPHORUS BONDS; OXYGEN ATOM; RELATIVE REACTIVITIES; SELECTIVITY;

EID: 79952634276     PISSN: 18614728     EISSN: 1861471X     Source Type: Journal    
DOI: 10.1002/asia.201000840     Document Type: Article
Times cited : (45)

References (126)
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    • Examples of asymmetric synthesis of biologically active and related compounds
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    • Reviews concerning reagents in synthesis
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    • Selected examples on the preparation of ligands
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    • The final product is exactly the same for both mechanisms in the case of the symmetrical alkyne; the products may be the same or may differ in the case of the unsymmetrical alkyne (see Refs. [8, 9] for discussion)
    • The final product is exactly the same for both mechanisms in the case of the symmetrical alkyne; the products may be the same or may differ in the case of the unsymmetrical alkyne (see Refs. [8, 9] for discussion).
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    • 3Cl] for M=Rh
    • 3Cl] for M=Rh.
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    • Some useful data may be obtained by considering the regioselectivity of the reactions of terminal alkynes or unsymmetrical internal alkynes, however, interpretations of observed regioselectivity usually depends on empirical relationships taken for granted. These mechanistic considerations will not be repeated here (see Refs. [8, 9, 12-15])
    • Some useful data may be obtained by considering the regioselectivity of the reactions of terminal alkynes or unsymmetrical internal alkynes, however, interpretations of observed regioselectivity usually depends on empirical relationships taken for granted. These mechanistic considerations will not be repeated here (see Refs. [8, 9, 12-15]).
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    • note
    • With such a difference in the activation barriers, the direct product of acetylene insertion into the M-P bond should be higher in energy compared to complex III, if additional stabilization by coordination of the oxygen atom would not be present. This will be shown later with the substrate, where such additional coordination is not possible.
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    • 79957685787 scopus 로고    scopus 로고
    • note
    • For clarity reasons insertion into the M-H bond is omitted in Figure 1 b and 1 c, as the representations of the structures do not differ significantly from those shown in Figure 1 a. Geometry data for all studied reactions are provided in Table 2.
  • 96
    • 79957763219 scopus 로고    scopus 로고
    • See Figure S1 in the Supporting Information for the structures involved in the Rh system. A similar nature of the transition states was found, but with the difference that Rh complexes adopted a pyramidal geometry arrangement, while Pd, Ni, and Pt complexes possessed square-planar or T-shaped geometries
    • See Figure S1 in the Supporting Information for the structures involved in the Rh system. A similar nature of the transition states was found, but with the difference that Rh complexes adopted a pyramidal geometry arrangement, while Pd, Ni, and Pt complexes possessed square-planar or T-shaped geometries.
  • 97
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    • note
    • 2=CH->σ-CH(P)=CH-≤laquo;π-HC≡CH (where P is a phosphorus group).
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    • The same orientation of the P=O group in these transition states was employed for comparison
    • The same orientation of the P=O group in these transition states was employed for comparison.
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    • note
    • 2 group, but this was not addressed in the present study. For comparison, a similar procedure to optimize the structures of products was utilized for all complexes.
  • 100
    • 79957778834 scopus 로고    scopus 로고
    • Either direct isomerization or a dissociative mechanism (i.e. alkyne dissociation, isomerization of T-shaped [M(H)(P)(L)] species, and alkyne recoordination) can be involved
    • Either direct isomerization or a dissociative mechanism (i.e. alkyne dissociation, isomerization of T-shaped [M(H)(P)(L)] species, and alkyne recoordination) can be involved.
  • 101
    • 79957750602 scopus 로고    scopus 로고
    • In fact, metal hydrides may be destroyed in the presence of acids (even catalytic amounts of acid) and this procedure was utilized to control the regioselectivity of the reaction (see Refs. [8, 9])
    • In fact, metal hydrides may be destroyed in the presence of acids (even catalytic amounts of acid) and this procedure was utilized to control the regioselectivity of the reaction (see Refs. [8, 9]).
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    • -1 for the transition states corresponding to acetylene insertion into the M-H bond (IV-TS and X-TS)
    • -1 for the transition states corresponding to acetylene insertion into the M-H bond (IV-TS and X-TS).
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    • M. J. Frisch and co-workers: Gaussian 03, Gaussian, Inc., Pittsburgh PA, 2003
    • M. J. Frisch and co-workers: Gaussian 03, Gaussian, Inc., Pittsburgh PA, 2003.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.