|
ИСТИНА |
Войти в систему Регистрация |
ИСТИНА ИНХС РАН |
||
Transition Metals Complexes of Naphthalene: DFT Studies of Structures, Reactivity and Dynamic Behaviour (pp. 93-126)книга
- Авторы: OprunenkoYF, Gloriozov IP
- Год издания: 2011
- Место издания: Nova Publisher USA
- Объём: 33 страниц
- Аннотация: Quantum chemical modeling (DFT - nonempirically constructed PBE functional and extended TZ2p split basis sets for valence electrons and SBK-JC pseudopotentials for core electrons) was used for the investigation of structure, reactivity and dynamic behavior such as rotation and intra- and inter-ring haptotropy n n in naphthalene transition metal (Ni, Ir and Cr) complexes with different hapticities n(n=2, 4, 6).For chromium tricarbonyl complexes theoretical reaction paths were calculated for inter-ring haptotropic 6,6-rearrangements when organometallic group intermolecularly moves from one ring to another accompanied with the rotation of the metalcarbonyl fragment in the regioisomeric complexes. The structures and energy characteristics of stationary points of the systems were determined. The migration of the Cr(CO)3 group was shown to occur at the periphery of the ligand via transition states with the structure of 3-allylic or 4-trimethylmethane complexes. Calculated geometries of the complexes and the activation barriers were in a close agreement with the experimental data. The reactivity of 6-tricarbonylchromium complex of naphthalene with n-BuLi (lithiation) was also studied by the DFT. The kinetic and thermodynamic factors that control the direction and selectivity of metallation were calculated for the model 6- C10H8Cr(CO)3. Both approaches indicate that lithiation occurs exclusively at the aromatic ring bonded to the transition metal, which agrees with the experimental data. The selectivity inside this ring is governed by a thermodynamic factor. The solvation effects were simulated for the lithium salt of the model 6- naphthalenechromium tricarbonyl complex in which lithium is localized at the α(1)- position of coordinated ring. The simulation showed the most stable coordination of the lithium atom with two THF molecules.
- Добавил в систему: Опруненко Юрий Федорович