chemia - Studia

RALUCA O. POP, MIHAI MEDELEANU, MIRCEA MRACEC
Concerning the use of the magnetic criteria to evaluate the aromaticity,
one of the most used indices is NICS (Nucleus Independent Chemical Shift) [4],
computed at the center of the molecule (NICS(0)) or at 1Å distance above
the molecule’s geometric center. Recent work of Martin et al. [5, 6] report
the use of computed NMR shielding effects on a molecular probe (a diatomic
hydrogen molecule, placed at a 2-2.5 Å above the geometric center of the ring)
in order to evaluate the aromatic character of fused hydrocarbons. The same
methodology was applied to the heterobenzenes of series (λ 3 -X-λ 3 -Y) 3 (where
X, Y = CH, N, P, As) and the shielding values of different heterobenzenes on
the diatomic hydrogen probe (placed at 2.5 Å above the center of molecule)
were compared with NICS(2.5) values. Moving the H 2 probe along x and y
coordinates of the geometric center of the rings (step size 0.5 Å, three steps in
each direction) leads to a complete evaluation of the shielding/deshielding
effects.
Y
X
Y
X
X
Y
X, Y: CH, N, P, As
Figure 1. General formula of the heterobenzenes (λ 3 -X-λ 3 -Y) 3
RESULTS AND DISCUSSION
In a previous paper [3] we reported the evaluation of the aromatic
character of the same heterobenzenes series using bond length- and bond
order-based indices. No concluding results were obtained, mostly due to
the D 3h and D 6h symmetry of the compounds that strongly influences the
values of bond length- and bond order-based indices. A possible method
for avoiding such situation is the use of geometric angle-based indices.
Doerksen et al. [7, 8] mentioned two indices based on alternance of
the angles, namely AVGNEXT and ADIFFPC and they assigned the maximum
value (100) to benzene ring and the minimum value (0) to a six-membered cycle
with alternant angles of 110° and 130°, respectively. For the heterobenzene
series of this study, the minimum value will correspond to a six-membered
cycle with alternant angles of 100° and 135°, respectively.
n
⎡ 1
⎤
AVGNEXT = 100 ⎢1 − θi
θ
i + 1
35
∑ −
n
⎥
(1)
⎣
i ⎦
1 n
ADIFFPC 100 ⎡ 1 ( ) 2 ⎤
= ⎢ − θmed
−θi
1837.5
∑ ⎥
(2)
⎣
i
⎦
148