Nucleus-independent chemical shift profiles along the intrinsic distortion path for Jahn–Teller active molecules. Study on the cyclopentadienyl radical and cobaltocene
J. Serb. Chem. Soc. 80 (7) 877–888 (2015) UDC 547.514.72+546.732:547.521+
JSCS–4766 519.677:544.112–185
Original scientific paper
877
Nucleus-independent chemical shift profiles along the intrinsic
distortion path for Jahn–Teller active molecules. Study on the
cyclopentadienyl radical and cobaltocene
LJUBICA ANDJELKOVIĆ1, MARKO PERIĆ1#, MATIJA ZLATAR1
and MAJA GRUDEN-PAVLOVIĆ2*#
1Center for Chemistry, ICTM, University of Belgrade, Njegoševa 12, 11001 Belgrade, Serbia
and 2Faculty of Chemistry, University of Belgrade, Studentski Trg 12–16,
11001 Belgrade, Serbia
(Received 7 November 2014, revised 11 March, accepted 12 March 2015)
Abstract: The aromatic/anti-aromatic behavior of the cyclopentadienyl anion
(Cp-), bis(η5-cyclopentadienyl)iron(II) (Fe(Cp)2), as well as of the Jahn–Teller
(JT) active cyclopentadienyl radical (Cp•) and bis(η5-cyclopentadienyl)-
cobalt(II) (Co(Cp)2) were investigated using density functional theory (DFT)
calculations of the nuclear independent chemical shifts (NICS). According to
the NICS values, pentagon ring in Fe(Cp)2 is more aromatic than that of the
isolated Cp-. The NICS parameters were scanned along the Intrinsic Distortion
Path (IDP) for Cp• and Co(Cp)2 showing anti-aromaticity, which decreased
with increasing deviation from the high symmetry D5h to the low symmetry
(LS) C2v. Changes in the NICS values along the IDP revealed that Co(Cp)2 in
the LS nuclear arrangement has aromatic character, in contrast to the case of
Cp•.
Keywords: vibronic coupling; DFT; aromaticity; metallocene.
INTRODUCTION
Aromaticity, an intuitive concept in chemistry and physics, is considered as a
property of systems that are thermodynamically stabilized due to cyclic electron
delocalization. The delocalized electronic structure of aromatic compounds
yields enhanced planarity, equalized bond lengths, enhanced stability due to the
resonance, favoring substitution instead of addition that would be typical for
isolated double bonds, and the ability to sustain ring currents when exposed to
external magnetic fields. Contrary to the concept of aromaticity, the Jahn–Teller
(JT) effect1,2 induces unequalization of bond lengths, leading to the stabilization
* Corresponding author. E-mail: gmaja@chem.bg.ac.rs
# Serbian Chemical Society member.
doi: 10.2298/JSC141107025A
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878 ANDJELKOVIĆ et al.
of a system upon distortion. The connection of aromaticity and the JT effect is of
utmost importance, since both effects have been very useful in the character-
ization and interpretation of the structure, stability and reactivity of many mole-
cules. For this reason, computational chemists seek the origin, explanation and
understanding of these two phenomena. According to The Hückel molecular
orbital (MO) theory,3,4 species with 4n + 2 π electrons are aromatic, whereas
structures with 4n π electrons are defined as anti-aromatic. Structures with 4n+1
π electrons with unpaired electrons in degenerate orbitals are JT active species,
and are supposed to show anti-aromaticity.5–8 Bearing in mind that the JT theo-
rem states that a molecule with a degenerate ground electronic state distorts along
non-totally symmetric vibrational coordinates, and in such a way removes the
degeneracy and lowers the energy, the question naturally arises: How does the JT
distortion influence the aromaticity/anti-aromaticity? Although it is well known
that different criteria of aromaticity may lead to different overall conclusions,9
nucleus-independent chemical shifts (NICS) provide a widely accepted quanti-
tative measure of aromaticity/anti-aromaticity.10,11 Furthermore, a scan of the NICS
parameters along the intrinsic distortion path (IDP)12–14 was found to be the
method of choice in the analysis of the aromatic behavior of JT active spe-
cies,7,8,15 since the distortion path provides direct insight into the microscopic
origin, mechanism and consequences of distortion.13,14
А detailed density functional theory (DFT) computational analysis was per-
formed to investigate the aromaticity of the cyclopentadienyl anion (Cp–), bis(η5-
-cyclopentadienyl)iron(II) (Fe(Cp)2), the cyclopentadienyl radical (Cp
•) and bis-
(η5-cyclopentadienyl)cobalt(II) (Co(Cp)2). In spite of their relatively simple
composition, the aromaticity of the JT active Cp• and Co(Cp)2 have not been
fully rationalized so far. Therefore, the aim of this work was also to understand
the influence of the JT effect on the aromatic behavior of these species. The
NICS were determined for the reference non-JT active species, Cp– and Fe(Cp)2,
and molecules prone to the JT effect, Cp• and Co(Cp)2. In order to preserve
chemically important features, an analysis of the full NICS profile of Cp• and
Co(Cp)2 along the IDP was performed.
METHODOLOGY
All the DFT calculations were realized using the Amsterdam Density Functional prog-
ram package, ADF2013.01.16-18 Geometry optimization of all the investigated molecules was
performed using the local density approximation (LDA) characterized by the Vosko–Willk–
–Nusair (VWN) parametrization,19 as well as using general gradient approximations (GGA),
such as BP86,20,21 PW91,22 OPBE,23 and S12g,24 and hybrids B3LYP25,26 and S12h.24 All
electron triple-zeta Slater-type orbitals (STO) plus one polarization function (TZP) basis set
were used for all atoms. All calculations were spin-unrestricted. Analytical harmonic fre-
quencies27,28 were calculated in order to ascertain that the low symmetry (LS) structures cor-
respond to the stationary points on the potential energy surfaces. Calculations of the NICS
values were performed at the B3LYP/6-311+G* level of theory using the Gaussian 09W
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JAHN-TELLER EFFECT AND AROMATICITY 879
program package using LDA optimized geometries.21,29-31 The NICS parameters were cal-
culated for ghost atoms located at the center of Cp- and Cp•. In order to obtain the full profile
of aromatic/anti-aromatic behavior, calculations of the NICS parameters were performed from
0 Å to 5 Å, in steps of 0.5 Å. In order to avoid the influence of the magnetic field of the
central metal ion in metallocenes, the first NICS value was calculated 1 Å above the metal ion
along the z-axis. For JT active species in a high symmetry (HS) nuclear arrangement, the
NICS values were calculated imposing HS (D5h) nuclear arrangement and LS (C2v) of electron
density. The NICS parameters for JT active species, Cp• and Co(Cp)2, were scanned along the
IDP.
Intrinsic distortion path – IDP
The IDP method12-14 is based on the fact that all the information about the vibronic
coupling at the HS nuclear arrangement is also contained in the distorted LS minimum energy
structure. Hence, the distortion is given as a superposition of all totally symmetric normal
modes in the LS point group, linking the HS configuration with the LS structure. Every point
on the potential energy surface can be represented by a 3N dimensional vector, N being the
number of atoms, XR
, using mass-weighted generalized coordinates relative to the origin.
The geometry of the LS energy minimum obtained by DFT calculations was chosen to be the
origin of the configuration space, LS 0R =
. Within the harmonic approximation, it is possible
to express XR
as a linear combination of Na1 totally symmetric normal coordinates in the LS:
a1
1
N
X Xk k
k
R Qω
=
=
(1)
where ωXk are weighting factors that represent the contribution of the displacements along the
different totally symmetric normal coordinates to XR
; kQ
are mass-weighted totally sym-
metric normal coordinates, which are the eigenvectors of the Hessian, obtained from the DFT
frequency calculations in the LS minimum energy conformation. The corresponding eigen-
values are λk.
Within this model, the energy of any nuclear configuration XR
, EX, relative to the LS
energy minimum, is expressed as the sum of the energy contributions of all the LS totally
symmetric normal modes:
a1 a1
2 2
1 1
1
2
N N
X k kXk k
k k
E E Qω λ
= =
= =
(2)
The force at any given point ( XR
), XkF
is defined as a derivate of the energy over Car-
tesian coordinates and in the HS point, it indicates the main driving force for the JT distortion.
The total force is represented as a vector sum of the individual forces:
a1 a1
tot
1/ 2
1 1
1
2
N N
X Xk k k Xk
k k
F M Q Fω λ
= =
= =
(3)
where M is a diagonal 3N×3N matrix with atomic masses in triplicate as elements (m1, m1, m1,
m2,…, mn), and enables the calculation of the IDP exactly from the HS to the LS point. The
above details about IDP can be found elsewhere.12-14
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880 ANDJELKOVIĆ et al.
RESULTS AND DISCUSSION
The planar Cp– in its singlet state with D5h symmetry was optimized using
several different levels of theory. All chosen exchange correlation (XC) functi-
onals reproduced experimental geometrical parameters with sufficient accur-
acy,32 Table I. The Fe(Cp)2 molecule has two possible conformations, eclipsed
D5h and staggered D5d. According to previous studies, the D5h conformation is
the global minimum on the potential energy surface.33–38 The calculated bond
lengths, Table I, are in excellent agreement with the experimental data,39 and
with earlier theoretical investigations.40 Since all the functionals reproduced geo-
metrical parameters with good accuracy, the NICS were computed at the B3LYP/
/6-311+G* level, using geometries obtained with the simplest LDA functional.
Calculated NICS values for Cp– and Fe(Cp)2 are given in Table II. Previous
sophisticated computational studies provide a rather satisfactory insight into the
nature of the aromaticity of Cp– and revealed that Cp– is aromatic, which is in
accordance with the herein presented results.41–46 It is important to emphasize
that the NICS parameters for Cp– were computed at the center of the pentagon
and at various distances from the center of the ring. In the case of Fe(Cp)2, the
starting point for the NICS calculation was 1 Å above the central metal ion fol-
lowing the z-axis. The NICS value calculated at 1.6 Å represent the NICS in the
center of the pentagon ring of the cyclopentadienyl ligand. According to the
results, both molecules show aromatic character, and Fe(Cp)2 is more aromatic,
TABLE I. Selected bond lengths (Å) for the stationary points of the investigated molecules,
calculated with different XC functionals
Molecule Bond LDA BP86 PW91 OPBE S12g B3LYP S12h Exp.
Cp– (D5h,
1A1′) C–C 1.406 1.420 1.417 1.413 1.414 1.410 1.404 1.413
32
Fe(Cp)2 (D5h,
1A1′) Fe–C 2.004 2.055 2.049 2.006 2.033 2.082 2.048 2.03
39
C–C 1.422 1.434 1.432 1.429 1.429 1.422 1.417 1.4339
Cp· (C2v,
2B1) C–C 1.364
1.424
1.374
1.439
1.372
1.436
1.370
1.432
1.371
1.432
1.365
1.432
1.360
1.426
–
Cp· (C2v,
2A2) C–C 1.455
1.390
1.471
1.402
1.468
1.400
1.462
1.397
1.463
1.397
1.465
1.394
1.457
1.389
–
Co(Cp)2 (C2v,
2B1) Co–C 2.029
2.070
2.098
2.091
2.134
2.155
2.084
2.128
2.149
2.038
2.080
2.108
2.070
2.112
2.135
2.129
2.175
2.185
2.092
2.137
2.151
2.11950
C–C 1.434
1.415
1.402
1.447
1.426
1.412
1.445
1.424
1.410
1.441
1.421
1.408
1.441
1.421
1.408
1.435
1.415
1.400
1.429
1.409
1.396
1.42950
Co(Cp)2 (C2v,
2A2) Co–C 2.090
2.047
2.022
2.150
2.111
2.083
2.143
2.104
2.076
2.101
2.056
2.031
2.129
2.089
2.062
2.184
2.153
2.118
2.149
2.115
2.083
2.11950
C–C 1.406
1.426
1.438
1.416
1.438
1.450
1.414
1.436
1.448
1.412
1.432
1.444
1.412
1.432
1.444
1.404
1.427
1.439
1.400
1.421
1.432
1.42950
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JAHN-TELLER EFFECT AND AROMATICITY 881
Table II.41–49 The isolated Cp– ring has a NICS value of –12.52 ppm in the
center, Table II. When two Cp– rings are placed at the distance which they have
in the Fe(Cp)2 molecule (3.2 Å), the NICS parameter calculated at the center of
one 5-membered ring was –12.13 ppm. Hence, the difference between the NICS
parameters for the isolated Cp– and for the Cp– fragment in Fe(Cp)2 is caused by
the presence of the central metal ion.
TABLE II. Calculated NICS values (ppm) for Cp- and Fe(Cp)2 using LDA optimized
geometries at various distances (Å) from the center of the molecules (for Fe(Cp)2, the NICS
calculated at 1.6 Å corresponds to the NICS value at the center of the Cp- ligand)
Distance, Å NICS NICSzz
Cp-
0.0 –12.52 –15.95
1.0 –9.44 –33.70
2.0 –3.97 –17.86
3.0 –1.63 –7.87
4.0 –0.77 –3.87
5.0 –0.40 –2.13
Fe(Cp)2
1.0 –103.47 –65.35
1.6 –42.14 –29.40
2.0 –31.15 –29.73
3.0 –9.46 –29.07
4.0 –2.44 –13.37
5.0 –0.95 –6.38
It is worth noting that Cp• and Co(Cp)2 have a hole and an unpaired electron,
respectively, in a doubly degenerate highest occupied molecular orbital. Since it
was previously shown that the eclipsed conformation is more stable and the JT
effect does not depend on the rotation of the rings,51 the discussion will be
limited only to Co(Cp)2 in the eclipsed conformation. The ground electronic state
of the investigated species in D5h symmetry is 2E1″, which couples with the
doubly degenerate vibration, e2′. According to group theory considerations, the
descent in symmetry goes from the D5h to the C2v point group, and thus, the state
2E1″ splits into 2A2 and 2B1. The average bond distances for the distorted LS
structures of Cp• calculated at different levels of theory are consistent, Table I.
The calculated bond lengths for Co(Cp)2 are in accordance with experiments,50
regardless of the choice of selected XC functional, Table I. Recently, the JT
distortion in these molecules was analyzed in detail using a multideterminental
DFT approach and the IDP method.12,14,51–53 The calculated JT parameters of
Cp• and Co(Cp)2 using a multideterminental DFT approach are given in Table
III. The results for Cp• obtained by Miller et al., who used dispersed fluorescence
spectroscopy, are considered to be the benchmark (EJT = 1237 cm–1).54 The pre-
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882 ANDJELKOVIĆ et al.
sent calculations at the LDA level gave a value of 1244 cm–1, which is in great
accordance with the experimentally obtained one, although all other XC functi-
onals also give satisfactory results, Table III. The values of the JT stabilization ener-
gies in Co(Cp)2, Table III, are in agreement with the value of 1050 cm–1 esti-
mated from its solid state EPR spectra.55 For both investigated JT active mole-
cules, the warping barrier is close to zero, independent of the level of theory
(Table III). The different ground states obtained by different XC functionals
(Table III) are due to the very small warping barriers, which are within the range
of the accuracy of the calculation. Furthermore, IDP analysis gave a deeper
insight into the vibronic coupling in these JT active molecules.14,53 In both mole-
cules, it is possible to distinguish two distinct regions on the potential energy
profile. In the first region, the energy changes faster, and most of the EJT is
achieved after 40 % of the path. In the second region, the change of the energy is
small, the adiabatic potential energy surface is flat and the molecule just relaxes
towards the global minimum. Three vibrations are most important for the dis-
tortion in Cp: C–C stretch, C–C–C bend, and C–C–H bend. These three modes
were experimentally found to be the most significant.54 In the case of Co(Cp)2,
the out-of-plane ring deformation and C–H wagging (the out-of-plane C–H bend-
ing), are the most important for the JT distortion. Although the JT effect in Cp•
TABLE III. Results of the DFT calculations performed to analyze the JT effect in Cp•·and
Co(Cp)2; the energies are given in eV; the JT parameters EJT and Δ are given in cm
-1 and RJT
in (amu)1/2Å
Molecule Symmetry LDA BP86 PW91 OPBE S12g B3LYP S12h
Cp• D5h,
2E1″ –64.674 –59.989 –61.008 –60.966 –61.624 –67.948 –72.863
D5h,
2A2 –64.653 –60.031 –61.042 –61.018 –61.658 –68.369 –73.402
D5h,
2B1 –64.653 –60.031 –61.042 –61.018 –61.658 –68.369 –73.402
C2v,
2A2 –64.808 –60.192 –61.203 –61.179 –61.817 –68.578 –73.596
C2v,
2B1 –64.808 –60.192 –61.205 –61.179 –61.817 –68.578 –73.596
EJT,
2A2 1244.5 1301.8 1294.5 1300.2 1281.6 1685.7 1567.9
EJT,
2B1 1244.5 1301.0 1312.3 1301.0 1284.0 1688.1 1568.8
Δ 0.0 –0.8 –17.7 –1.6 –2.41 0.0 0.8
RJT,
2A2 0.25 0.26 0.26 0.26 0.26 0.27 0.27
RJT,
2B1 0.25 0.26 0.26 0.26 0.26 0.27 0.27
Co(Cp)2 D5h,
2E1″ –142.290 –130.675 –133.049 –133.385 –134.525 –149.601 –161.584
D5h,
2A2 –142.261 –130.690 –133.061 –133.381 –134.528 –150.140 –162.247
D5h,
2B1 –142.261 –130.690 –133.061 –133.381 –134.528 –150.140 –162.246
C2v,
2A2 –142.362 –130.785 –133.156 –133.485 –134.626 –150.230 –162.345
C2v,
2B1 –142.362 –130.785 –133.156 –133.485 –134.626 –150.231 –162.344
EJT,
2A2 813.8 762.2 761.4 838.0 783.9 727.5 791.2
EJT,
2B1 813.8 761.4 759.8 839.6 785.6 729.1 785.6
Δ 0.0 0.0 1.6 –1.6 0.0 –2.4 13.7
RJT,
2A2 0.35 0.34 0.34 0.35 0.34 0.34 0.34
RJT,
2B1 0.35 0.34 0.34 0.35 0.34 0.34 0.34
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JAHN-TELLER EFFECT AND AROMATICITY 883
and Co(Cp)2 has often been studied,54–56 the influence of the vibronic coupling
on their aromatic character has not been investigated. The question is whether the
distortion has a significant impact on the change of aromaticity. In Cp• and
Co(Cp)2, the degeneracy of the 2E1″ state is broken by the JT distortion that
stabilizes the system. Therefore, the NICS parameters were computed at the LDA
optimized geometries for both the HS and LS points on the potential energy
surfaces. Observing the NICS values at the HS point of Cp•, a high anti-aromatic
character is noticeable, Table IV. The calculated parameters for the global mini-
mum of Cp• show that it still possesses anti-aromatic character,5 but much
weaker than in the HS point, Table IV. Moving from the center of the pentagon
ring along the z-axis, the NICS indices decrease. In the case of Co(Cp)2, it is
evident that molecule at the HS point has high anti-aromatic character, Table V.
In the global minimum structure, Co(Cp)2 shows σ aromaticity and π anti-arom-
aticity according to the NICS and NICSzz values, Tables IV and V.
TABLE IV. Calculated NICS values (ppm) for Cp• using LDA optimized geometries at HS
and LS geometries at various distances (Å) from the center of the ring; the NICS values for
both LS structures are the same
Electronic state Distance, Å NICS NICSzz
Cp• (D5h)
2B1/
2A2 0.0 86.88 273.95
1.0 72.10 217.30
2.0 21.36 61.38
3.0 6.65 18.12
4.0 2.69 7.06
5.0 1.34 3.40
Cp• (C2v)
2B1/
2A2 0.0 20.78 77.09
1.0 14.79 45.84
2.0 3.58 8.00
3.0 0.91 0.87
4.0 0.31 –0.12
5.0 0.13 –0.22
Since dependence of the NICS parameters on the distortion, /X JTR R
, and
distances (Å) from the center of the molecules gives a more detailed picture, the
NICS parameters were monitored along the IDP path for Cp• and Co(Cp)2, Fig. 1
and 2, respectively. The NICS parameters were scanned only for the 2B1 state,
since those computed for the 2A2 state were almost the same. Due to the non-
totally symmetric electron density, both molecules in D5h possess strong anti-
aromatic character. Near the point of electron degeneracy, i.e., near the HS
nuclear arrangement, the HOMO–LUMO gap is substantially small, thus the
NICS parameters have large positive values in the first region of the IDP (Figs. 1
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884 ANDJELKOVIĆ et al.
TABLE V. Calculated NICS values (ppm) for Co(Cp)2 using LDA optimized geometries at
HS and LS geometries at various distances (Å) from central metal ion. The NICS value
calculated at 1.7 Å corresponds to the NICS parameter in the center of the pentagon in
Co(Cp)2; The NICS values for both LS structures are the same
Electronic state Distance, Å NICS NICSzz
Co(Cp)2 (D5h)
2B1/
2A2 1.0 302.49 1135.98
1.7 67.59 281.61
2.0 42.20 182.76
3.0 24.86 73.78
4.0 9.80 24.48
5.0 4.04 9.32
Co(Cp)2 (C2v)
2B1/
2A2 1.0 –3.91 209.45
1.7 –10.86 42.41
2.0 –11.11 21.41
3.0 –1.64 –5.91
4.0 –0.10 –5.08
5.0 –0.04 –2.92
Fig. 1. Schematic plot of the NICS values along the IDP for Cp• (from D5h to C2v),
2B1/
2A2
electronic states.
and 2). Going toward the global minimum point on the potential energy surface,
the NICS values decrease and hence, the initially strong anti-aromatic character
lowers, and finally, in the case of Co(Cp)2, the NICS indices become negative, Figs.
1 and 2. It is worth noting that the negative NICS values in Co(Cp)2 occur after
40 % of the IDP, where most of the JT stabilization is attained. The driving force
responsible for the removal of orbital degeneracy leads to an enlargement of the
HOMO–LUMO gap. Considering Cp•, for both the HS and LS nuclear arrange-
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JAHN-TELLER EFFECT AND AROMATICITY 885
ment, the calculations revealed that the NICS decrease gradually along the z-axis,
Fig. 1. Moving apart along the z-axis in the HS configuration of Co(Cp)2, an
abrupt decrease in the NICS parameters was observed until a distance of 1.7 Å
(center of pentagon ring), Fig. 2. Going even further, the NICS parameters show
a smooth decreasing trend, as expected.
Fig. 2. Schematic plot of the NICS values along the IDP for Co(Cp)2 (from D5h to C2v),
2B1/
2A2 electronic states.
CONCLUSIONS
Aromaticity is one of the oldest and most fundamental concepts in chem-
istry. The nature of aromatic compounds is very attractive, thus these species are
among the most desirable synthetic targets. Since aromaticity is still awaiting
comprehensive investigation, a detailed analysis of the NICS parameters, as one
of the most widely used and efficient magnetic criteria, was performed in Cp–,
Fe(Cp)2, Cp
• and Co(Cp)2 by the means of DFT.
The calculations revealed that Cp– and Fe(Cp)2 are highly aromatic mole-
cules. According to the NICS, the Cp– ring in Fe(Cp)2 is far more aromatic than
the isolated Cp–, showing the impact of the Fe2+. In other words, these results
would be highly attractive in applied sciences for the design of new advanced
materials with desired properties, and the understanding of electronic structure,
chemical bonding and properties in a moiety of aromatic species.
A thorough study of the influence of the JT effect on the aromaticity is pre-
sently of the utmost importance due to the increasing development of material
chemistry, and substantial differences in aromatic/anti-aromatic behavior of JT
active molecules. Thus, finding a method of choice to determine both chemically
relevant phenomena is essential since they lead to the different reaction pathways
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886 ANDJELKOVIĆ et al.
and the connection of aromaticity and vibronic coupling demands tremendous
caution. For this purpose, the monitoring of the NICS along the IDP was per-
formed. Similarly to the previous studies,7,8,15 the anti-aromaticity decreases
with increasing deviation from the high symmetry D5h structures to the low
symmetry C2v global minimum structures, confirming that the JT distortion rep-
resents a mechanism for reducing anti-aromatic character. In the LS structure of
Co(Cp)2, the NICS become even negative, revealing aromatic character, in con-
trast to Cp•.
Acknowledgement. This work was financially supported by the Ministry of Education,
Science and Technological Development of the Republic of Serbia (Grant No. 172035).
И З В О Д
ПРОФИЛ ХЕМИЈСКИХ ПОМЕРАЊА НЕЗАВИСНИХ ОД ЈЕЗГРА ДУЖ СВОЈСTВЕНОГ
ПУТА ДИСТОРЗИЈЕ ЗА МОЛЕКУЛЕ ПОДЛОЖНЕ ЈАН–ТЕЛЕРОВОЈ ДИСТОРЗИЈИ.
ПРОУЧАВАЊЕ ЦИКЛОПЕНТАДИЕНИЛ РАДИКАЛА И КОБАЛТОЦЕНА.
ЉУБИЦА АНЂЕЛКОВИЋ1, МАРКО ПЕРИЋ1, МАТИЈА ЗЛАТАР1 и МАЈА ГРУДЕН-ПАВЛОВИЋ2
1Центар за хемију, ИХТМ, Универзитет у Београду, Његошева 12, 11001 Београд и 2Хемијски
факултет, Универзитет у Београду, Студентски трг 16, 11001 Београд
Ароматичност/антиароматичност циклопентадиенил анјона (Cp
-
), бис(η5-цикло-
пентадиенил)гвожђа(II) (Fe(Cp)2), као и, циклопентадиенил радикала (Cp
•) и бис(η5-
-циклопентадиенил)кобалта(II) (Co(Cp)2), молекула подложних Јан–Телеровој дистор-
зији, испитивана је коришћењем теорије функционала густине (DFT) за израчунавање
хемијских померања независних од језгра (NICS). На основу израчунатих хемијских
померања, петочлани прстен у Fe(Cp)2 је ароматичнији него изоловани Cp
-
. NICS вред-
ности, праћене дуж својственог пута дисторзије за Cp• и Co(Cp)2, указују на антиарома-
тичност испитиваних врста, која се смањује са снижењем симетрије од D5h до C2v. Про-
мене у NICS параметрима дуж пута дисторзије показују да Co(Cp)2 у ниској симетрији
поседује ароматични карактер, за разлику од Cp•.
(Примљено 7. новембра 2014, ревидирано 11. марта, прихваћено 12. марта 2015)
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/ENU (Use these settings to create Adobe PDF documents best suited for high-quality prepress printing. Created PDF documents can be opened with Acrobat and Adobe Reader 5.0 and later.)
>>
/Namespace [
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(Common)
(1.0)
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/OtherNamespaces [
<<
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(4.0)
]
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/SimulateOverprint /Legacy
>>
<<
/AddBleedMarks false
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/ConvertColors /ConvertToCMYK
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/FlattenerPreset <<
/PresetSelector /MediumResolution
>>
/FormElements false
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>>
]
>> setdistillerparams
<<
/HWResolution [2400 2400]
/PageSize [612.000 792.000]
>> setpagedevice