Spin uncoupling in methane activation

• Autorzy: Minaev B. F.
• Języki publikacji: EN

Abstrakty

EN

Activation of the C-H bond in methane by interaction with transition metal (TM) atom and organometallic complex can be considered by correlation diagram which involves the triplet 3(oo*) excited state localized on the activated bond in combination with the high-spin state of the TM species. This correlation diagram explains why the low-spin state of the TM species is reactive to such a catalytic process, and why the high-spin state in nonreactive. Complexes of the type MCp(CO), where Cp = CsHs, M = Co, Rh, Ir, and their ability to activate the C-H bond of methane are considered in detail. Following calculations of Siegbahn and others the isovalent complex of cobalt (M = Co) is entirely inert toward methane in contrast to the rhodium and iridium systems. At the same time all complexes are active in reaction with the CO molecule. In addition to Siegbahn's explanation of the triplet ground state nature of the cobalt complex, spin-orbit coupling analysis is given, which demonstrates the importance of spin uncoupling in the singlet state reactivity. A similar concept can be applied for methane activation processes by bare TM atoms.

Słowa kluczowe

EN

methane; spin-orbit coupling

PL

metan; spin

• Wydawca: Centrum Upowszechniania Nauki PAN
• Czasopismo: Bulletin of the Polish Academy of Sciences. Chemistry
• Rocznik: 2000
• Tom: Vol. 48, No. 2
• Strony: 131--143
• Opis fizyczny: Bibliogr. 32 poz.

Twórcy

autor

Minaev B. F.

• Chemistry Department, Cherkassy Institute of Engineering and Technology, BVD. Shevchenko 460, 257006 Cherkassy, Ukraine