Theoretical Studies of Transition Metal Carbene Complexes (Reactivities, Electronic Structures, and Diels-Alder Reaction) 


Vol. 36,  No. 1, pp. 3-15, Feb.  1992


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  Abstract

크롬이움, 몰리브덴늄, 텅그스텐의 carbene 착물인 (CO)5Cr=CCHCH2(XCH3), (CO)5Mo=CCHCH2(XCH3), (CO)5W=CCHCH2(XCH3)에 대해서 확장된 Huckel 방법으로 계산하여 이들의 전자구조와 반응성 등을 고찰하였다. fragment들의 궤도함수 상관도로부터 M=Ccarb 이중결합의 특성을 알 수 있다. M=Ccarb 이중결합의 σ결합은 carbene의 HOMO로부터 (CO)5M의 LUMO로 전자가 이동하므로 형성되고 π결합은 전이금속의 축퇴된 dπ 궤도함수로부터 carbene의 LUMO로 전자가 역이동하므로서 형성된다. M=Ccarb 결합에서 전하분극은 Mo, W-착물에 대해서 M쪽이 더욱 양으로 계산되었다. 화학적 또는 물리적 성질은 carbene 탄소원자의 양전하에 의하여 결정되며 carbene 탄소원자의 친전자적 반응성은 전하에 의해서가 아니라 frontier orbital의 LUMO에 의해서 지배받는다. Electronic structures and reactivities of the chromium, molybdenum, and tungsten carbene complexes, (CO)5Cr=CCHCH2(XCH3), (CO)5Mo=CCHCH2(XCH3), and (CO)5W=CCHCH2(XCH3), are studied by means of Extended Huckel calculations. The origin of the M=Ccarbene double bond is clarified from the diagram of the orbital correlation with the fragment orbitals. The σ bond of the M=Ccarbene double bond is formed by the electron transfer interaction from the HOMO of the carbene to the LUMO of the (CO)5M. The π bond is formed through the back-transfer of electrons from one of the degenerated dπ orbitals to the LUMO of the carbene. The polarization of charge of the M=Ccarbene bond is calculated to be M=Ccarbene for Mo, and W carbenes. The chemical and physical properties of these complexes are resulted from an appreciable positive charge on the carbene carbon. The electrophilic reactivity of the carbene carbon is not charge controlled, but is controlled by the frontier orbital, LUMO.

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  Cite this article

[IEEE Style]

S. Park, I. Kim, J. Kim, S. Kim, C. Choi, Y. Cheun, "Theoretical Studies of Transition Metal Carbene Complexes (Reactivities, Electronic Structures, and Diels-Alder Reaction)," Journal of the Korean Chemical Society, vol. 36, no. 1, pp. 3-15, 1992. DOI: .

[ACM Style]

Seong-Kyu Park, Ill-Doo Kim, Joon-Tae Kim, Sung-Hyun Kim, Chang-Jin Choi, and Young-Gu Cheun. 1992. Theoretical Studies of Transition Metal Carbene Complexes (Reactivities, Electronic Structures, and Diels-Alder Reaction). Journal of the Korean Chemical Society, 36, 1, (1992), 3-15. DOI: .

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