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.