• Title/Summary/Keyword: C-H bond activation

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Theoretical Study of C-H σ-Bond Activation and Related Reactions

  • Sakaki, Shigeyoshi
    • Bulletin of the Korean Chemical Society
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    • v.24 no.6
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    • pp.829-831
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    • 2003

  • Various theoretical studies of σ-bond activation of organic molecules by transition metal complexes arereviewed. In the homolytic σ-bond activation, the d orbital energy level of the central metal is an importantfactor, as well known. At the same time, the electron-withdrawing substituent which stabilizes the sp3 orbitalaccelerates the homolytic σ-bond activation. In the heterolytic C-H σ-bond activation of RH by $MXL_n$, the XHbond formation is an important driving force, where $MRL_n$ and HX are formed as products. The heterolytic σ-bond activation is also understood in terms of the electrophilic attack of the metal center to the substrate.

  • https://doi.org/10.5012/bkcs.2003.24.6.829 인용 PDF KSCI

Density Functional Study on the C-H Bond Cleavage of Aldimine by a Rhodium(I) Catalyst

  • Yoo, Kyung-Hwa;Jun, Chul-Ho;Choi, Cheol-Ho;Sim, Eun-Ji
    • Bulletin of the Korean Chemical Society
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    • v.29 no.10
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    • pp.1920-1926
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    • 2008

  • We investigated the C-H bond activation mechanism of aldimine by the [RhCl$(PPH_3)_3$] model catalyst using DFT B3LYP//SBKJC/6-31G*/6-31G on GAMESS. Due to their potential utility in organic synthesis, C-H bond activation is one of the most active research fields in organic and organometallic chemistry. C-H bond activation by a transition metal catalyst can be classified into two types of mechanisms: direct C-H bond cleavage by the metal catalyst or a multi-step mechanism via a tetrahedral transition state. There are three structural isomers of [RhCl$(PH_3)_2$] coordinated aldimine that differ in the position of chloride with respect to the molecular plane. By comparing activation energies of the overall reaction pathways that the three isomeric structures follow in each mechanism, we found that the C-H bond activation of aldimine by the [RhCl$(PH_3)_3$] catalyst occurs through the tetrahedral intermediate.

  • https://doi.org/10.5012/bkcs.2008.29.10.1920 인용 PDF KSCI

Bond Orbital Theory of Chemical Reactivity (反應性의 結合 Orbital 理論)

  • Yang, Kang;Ree, Tai-Kyue
    • Journal of the Korean Chemical Society
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    • v.8 no.1
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    • pp.20-24
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    • 1964

  • The linear combination of bond orbitals method is used to investigate the reactivity of halomethanes in abstraction reactions by atoms. The activation energy is evaluated on the assumption that, in an activated complex, two electrons in a bond to be broken become completely isolated from the rest of the ${\sigma}$-electron systems. Such a model leads to an intuitively attractive concept that the interactions between the reactive bond and the neighboring bonds govern the reactivity of ${\sigma}$-electron systems. The resulting equation for the activation energy, ${\varepsilon},\;is:\;{\narepsilon}= ${\varepsilon}={\zeta}+$$${\sum}_{i=1}^3$${\eta}c-I,$ c-4 Here, subscript C-4 indicates the bond to be broken, while C-i represents the other three bonds surrounding the reactive bond; ξ is the activation energy of a hypothetical reaction of an isolated C-4 bond and an attacking atom; and ${\eta}$C-i,C-4 stems from the stabilizing interacting of C-4 bond with neighboring C-i bonds. A choie of η′s consistent with bond strength data simplifies the above equation to a form ${\varepsilon}={\zeta}\;+\;N{\eta}c$-H, C-4 where N denotes the number of C-H plus C-F bond in halomethanes. In agreement with this equation, experimental -values increase linearly with increasing N.

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