Laboratory Experiment

pubs.acs.org/jchemeduc

Understanding the Jahn−Teller Effect in Octahedral

Transition-Metal Complexes: A Molecular Orbital
View of the Mn(β-diketonato)3 Complex
Roxanne Freitag and Jeanet Conradie*
Department of Chemistry, P.O. Box 339, University of the Free State, 9300 Bloemfontein, Republic of South Africa
*
S Supporting Information

ABSTRACT: Density functional theory calculations are utilized to calculate

and visualize the compression and elongation Jahn−Teller distortion in
selected Mn(β-diketonato)3 complexes. Students often struggle to understand
this effect, due to the lack of visualization of the repulsion effect between
charges on the metal and the axial ligands. Here, a visualization of the
molecular orbitals involved in the elongation and compression Jahn−Teller
distortion provides a great understanding of the effect.

KEYWORDS: Graduate Education/Research, Upper-Division Undergraduate, Physical Chemistry, Laboratory Instruction,

Computer-Based Learning, Textbooks/Reference Books, Computational Chemistry, Molecular Properties/Structure

T he Jahn−Teller effect (JTE) is formally described as the

geometrical distortion of molecules and ions that are
associated with certain electron configurations. When a
molecule exhibits a spatially degenerate electronic ground
state, it will undergo a geometrical distortion that removes this
degeneracy to lower the overall energy of the species.1 The
Jahn−Teller effect is encountered both in organic compounds
(e.g., cyclobutadiene2,3 and cyclooctatetraene4) and in transition-
metal complexes (e.g., the hexaaquacopper(II) complex ion,
[Cu(OH2)6]2+5). This article focuses on the JTE observed in
octahedral transition-metal complexes. This exercise can be utilized
in the physical chemistry curriculum at the upper-level under-
graduate or introductory graduate level as a computational exercise
or a lecture to introduce the Jahn−Teller effect.
upon their orientation relative to the six ligand coordination
positions. Two d orbitals, dx2−y2 and dz2 (called the eg set),
which have lobes that point at the ligands, will ascend in energy,
due to the repulsion between electrons in the orbitals and the
negative charges of the ligands. To maintain the total energy,
the three d orbitals, dxy, dxz, and dyz (named the t2g set), which
have lobes that lie between ligands experiencing less repulsion,
will descend in energy. The 5-fold degeneracy among the d
orbitals is thus lifted.
For a high-spin d4 metal complex, there is one vacancy in the
eg orbital group, either in the dx2−y2 or in the dz2 orbital. The
two possible ways to fill these orbitals, d1x2−y2d0z2 or d0x2−y2d1z2,
are of equal energy (see Figure 1A,B). Similarly, for a d9 metal
complex, the two d2x2−y2d1z2 or d1 x2−y2d2z2 occupations of the eg

■ BACKGROUND
Jahn and Teller proved that no nonlinear molecule can be
stable in a degenerate electronic state. Such a molecule has to
be distorted to lower symmetry to break the degeneracy. In
octahedral complexes with nine d electrons (d9), low-spin d7,
and high-spin d4 metal electrons, this effect is more pro-
nounced. The d electrons of an isolated metal ion are equi-
energetic. If this transition-metal ion is placed in a hypothetical
spherical field equivalent to the sum of the charges on six
ligands, the energies of all five d orbitals would rise together
(degenerately) as a result of the repulsions between the
negative charges of the electrons in the metal orbitals and the
negative charges on the ligands. However, in a real octahedral
(Oh) environment, the energy of the orbitals relative to the
perturbed energy of the hypothetical spherical field depends
© 2013 American Chemical Society and
Division of Chemical Education, Inc.
orbital group are of equal energy (see Figure 1C,D). According
to Jahn and Teller, this electronic situation is not stable and the
octahedron must distort (be reduced in symmetry) in such a
way that the energy of the two electronic configurations as
mentioned are not equal. When looking for example at the
configuration of d0x2−y2d1z2 (d4) and d1x2−y2d2z2 (d9), the
ligand(s) along the z axis are much more screened from the
charge of the central metal ion than the other four ligands along
the x and y axes,6 because most of the electron density will be
concentrated in the dz2 orbital between the metal and the two
ligands on the z axis. Consequently, there will be greater
electrostatic repulsion between the electron(s) in the dz2 orbital
and the ligands along the z axis than between the electrons in
the t2g set of orbitals pointing between the axes and the ligands
Published: November 12, 2013
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Journal of Chemical Education
Figure 1. Presentation of the two possible ways of electron filling of
the d orbitals of (A) and (B) high-spin d4 octahedral metal complexes
and (C) and (D) d9 octahedral metal complexes.
on the x and y axes itself. The ligands on the z axis will thus
move further away from the central metal ion and thus lower
the symmetry (z-out or elongation Jahn−Teller distortion).
This causes the dz2 orbital to be more stable (lower in energy)
than the dx2−y2 orbital, as is shown in Figure 2. The opposite
Figure 2. The effect of z elongation and compression Jahn−Teller
distortion on the M−L bond lengths and energy of the eg and t2g set of
orbitals.
distortion is expected from the d2x2−y2d1z2 (d9) and d1x2−y2d0z2
(d4) configurations (namely, z-in or compression Jahn−Teller
distortion).
The effect that the Jahn−Teller distortion has on the M−L
bond lengths, as well as on the orbital energies, is illustrated in
Figure 2. A z-out or elongation Jahn−Teller distortion leads to
an elongation of the M−L bond lengths on the z axis or a
shortening of the bond lengths on the x and y axes. The z-in or
compression Jahn−Teller distortion causes just the opposite,
the shortening of M−L bond lengths on the z axis or the
elongation of the M−L bond lengths on the x and y axes.
The Jahn−Teller distortion can also be explained by the use
of point groups. If the symmetry of a complex is lowered, the
complex will belong to a point group of lower symmetry. When
there is a change in the point group of the complex, the d
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Laboratory Experiment
orbitals of the metal change in energy. The octahedral symmetry
Oh has no distortion. The t2g orbital, however, splits into an a and
e component when going from Oh to D3 symmetry. When any of
the degenerate e orbitals in D3 symmetry are partially occupied,
the system is Jahn−Teller unstable and it will spontaneously
distort to C2 symmetry. Under C2 symmetry, the degeneracy of
the e orbitals is split into a and b components to stabilize the
complex. A D3 distortion leads either to a flattening (z-in) of the
octahedron or to increasing (z-out) its height.7 High-spin
transition-metal complexes such as d2 and d4 species, as well as
d9 species, would be Jahn−Teller unstable and would therefore
spontaneously distort to C2 symmetry. Various low- and high-spin
octahedral complexes can show the Jahn−Teller effect, but the
distortion is more pronounced when the degeneracy occurs in the
eg orbital group, as these orbitals point directly toward the ligands.
Figures S1 and S2 (in the Supporting Information) show all the
different electronic states of both low- and high-spin octahedral
complexes, as well as indicating for which states the Jahn−Teller
effect is possible (namely, uneven occupation of the eg orbitals).
Students often struggle to fully grasp the Jahn−Teller effect,
as they see it as a complex theorem. This exercise illustrates the
JTE by the visualization of the density functional theory (DFT)
calculated highest-occupied molecular orbital (HOMO) of three
selected octahedral MnIII(β-diketonato)3 complexes, where the
β-diketonato ligands are acetylacetonato (CH3COCHCOCH3)−,
dibenzoylmethanato (C6H5COCHCOC6H5)− and hexafluoroace-
tylacetonato (CF3COCHCOCF3)−; see Figure 3 for the structure.
Figure 3. The structure of MnIII(β-diketonato)3 complexes. The
numbers refer to Mn−O bonds. The z axis is defined along the Mn−O
bonds 5 and 6 as indicated. R = CH3, C6H5, or CF3.
■ COMPUTATIONAL METHOD
Three octahedral MnIII(β-diketonato)3 complexes, with the β-diketonato
ligands being acetylacetonato (CH3COCHCOCH3)−, dibenzoylmetha-
nato (C6H5COCHCOC6H5)−, and hexafluoroacetylacetonato
(CF3COCHCOCF3)−, as well as MnII(CH3COCHCOCH3)3−,
were chosen for this study. All structures were optimized with the
ADF (Amsterdam Density Functional) 2012 program,8 using the
GGA (Generalized Gradient Approximation) functional OLYP
(Handy−Cohen and Lee−Yang−Parr),9,10 the TZP (Triple ζ
polarized) basis set,11 a fine mesh for numerical integration, a-spin-
unrestricted formalism, applying tight convergence criteria, using C2
or C1 symmetry as indicated. The OLYP functional proved to be a
good choice to correctly calculate the ground state of paramagnetic
complexes.12
■
STUDENT EXERCISE
This is a dry lab experiment. Students can work individually. A
student handout is provided in the Supporting Information. A
desktop computer with suitable DFT software13 is required. Three
dx.doi.org/10.1021/ed400370p | J. Chem. Educ. 2013, 90, 1692−1696
Journal of Chemical Education Laboratory Experiment

hours in total should be budgeted to familiarize the students with

the DFT software, to run three single-point calculations (of ca. 10 min
each on a desktop computer) on the provided optimized
coordinates, as well as for interpretation of the results. Take
note that if nonoptimized coordinates are used, full geometry
optimizations are required, which may run for 3−12 h each.
First, the students have to optimize high-spin S = 5/2
(sextet) MnII(CH3COCHCOCH3)3− without any symmetry
constraint (C1), to evaluate the optimized lowest-energy
geometry of this complex. An example input file is provided
in the Supporting Information. The input geometry was chosen
specifically to have elongated Mn−O bonds along the z axis
and to be without any symmetry.
Second, the students have to optimize high-spin S = 2 (quintet) Figure 4. ADF/OLYP optimized geometry and the electronic
MnIII(CH3COCHCOCH3)3, to find the geometry and energy of configuration of the high-spin (S = 5/2) state of MnII(CH3CO-
the ground state of complex MnIII(CH3COCHCOCH3)3 in C2 CHCOCH3)3−. Bond lengths shown in Å.
symmetry. An example input file is provided in the Supporting
Information. Once the optimized geometry is obtained, the Mn(CH3COCHCOCH3)3, where only one of the eg orbitals has
electron occupation has to be determined from the output file (A an electron, and two degenerate electronic states are possible,
49//46 and B 45//44). Manganese(III) octahedral complexes are Figure 1A or 1B. During the optimization of the high-spin (S = 2)
known to be high-spin complexes that undergo Jahn−Teller state of Mn(CH3COCHCOCH3)3, the geometry is distorted to
distortion7,14 because of the partial filling of the doubly degenerate break the degeneracy of the eg orbitals.
eg orbital group. The electron filling of the d orbitals of Mn(β- The geometry and HOMO of the DFT optimized ground
diketonato)3 is thus expected to be either t32gd1z2 or t32gd1x2−y2. electronic state of the Mn(CH3COCHCOCH3)3 complex are
The highest-occupied molecular d orbital (HOMO) of Mn(β- presented in Figure 5A and a summary of the bond lengths (see
diketonato)3 is therefore either dz2 or dx2−y2. Once the ground- Figure 3 for the numbering of the bonds) is tabulated in
state geometry is obtained, an alternative electron occupation can Table 1. The two bonds in the z direction are ca. 0.25 Å longer
be specified to obtain the geometry of the alternative Jahn−Teller than the other four bonds. The HOMO of this electronic state
distortion. This can be achieved by moving the electron in the is mainly of dz2 character, pointing directly in the directions of
HOMO (A49) of the ground-state geometry, from an A to a B the ligands on the z axis. The antibonding character between the
irreducible representation. The alternative occupation of the dz2 orbital of the manganese center and pz orbital of Oβ‑diketonato on
electrons (A 48//46 and B 46//44) should thus be included in the the z axis is clear and leads to an elongation Jahn−Teller distortion
second geometry optimization; see the Supporting Information for and subsequent elongation of the Mn−O bond lengths along the z
an example input file. Ensure the input geometry in both cases to axis (bond lengths 5 and 6 in Table 1).
be C2. The Supporting Information also provides the optimized The geometry and HOMO of Mn(CH3COCHCOCH3)3
coordinates of the dz2 and dx2−y2 electronic states. with the alternative electron filling of the d orbitals, t32gd1x2−y2,
Once the optimized geometries of both the ground state and the is illustrated in Figure 5B. Here the two bonds along the z axis
alternative electron occupation of MnIII(CH3COCHCOCH3)3 are
obtained, the students have to evaluate the bond lengths and
relative energies of the two electronic states and also have to create
a file to visualize the HOMO of each electronic state. The electronic
energy can be used as an approximation of free energy G, as the
difference between electronic energy and Gibbs free energy is small.
The electronic energy is printed at the end of the output file.
Results on MnIII(C6H5COCHCOC6H5)3 and MnIII(CF3CO-
CHCOCF3)3 are also provided and discussed, should additional
exercise for the students be needed. Alternatively, three groups
of students could each solve the two electronic states of one of
the three complexes, comparing the results.

■ RESULTS AND DISCUSSION

The DFT optimized geometry of the high-spin (S = 5/2) state
of the MnII(CH3COCHCOCH3)3− complex is presented in
Figure 4. It is observed that, although the bonds along the z axis
in the starting geometry were longer than the other four Mn−O
bonds, the optimized geometry gives an almost perfect octahedral
structure, with equal Mn−O bonds of 2.248 Å up to three decimal
values. For this complex, the eg orbitals have one electron each,
that is, having even eg occupation. This high-spin d5 configuration Figure 5. ADF/OLYP geometry and HOMO orbital of the optimized
(see the inset in Figure 4) is thus nondegenerate, symmetric, and Mn(CH3COCHCOCH3)3 complex: (A) the minimum energy
allowed. Therefore, the distorted symmetry in the input file is electronic ground state showing mainly dz2 character and (B) the
restored to an octahedron in the optimized geometry. However, alternative electronic occupation showing mainly dx2−y2 character.
this is not the case with the high-spin (S = 2) state of Bond lengths shown in Å.

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Journal of Chemical Education Laboratory Experiment

Table 1. Mn−O Bond Lengths of the Indicated Optimized Mn(β-diketonato)3 Complexes

Bond Lengtha (Mn−O)/Å
Complex 1 2 3 4 5 6 Energy/(kJ mol−1) Population (%)
Mn(CH3COCHCOCH3)3
compression JT 2.118b 2.118 2.121 2.121 1.944 1.944 3.6 21
elongation JT 1.974 1.974 1.993 1.993 2.245 2.245 0 79
Mn(C6H5COCHCOC6H5)3
compression JT 2.100 2.100 2.112 2.112 1.934 1.934 5.6 9
elongation JT 1.965 1.965 1.974 1.974 2.217 2.217 0 91
Mn(CF3COCHCOCF3)3
compression JT 2.117 2.117 2.129 2.129 1.949 1.949 3.5 19
elongation JT 1.998 1.998 1.970 1.970 2.240 2.240 0 81
a
Refer to Figure 3 for Mn−O numbering. bElongated bond lengths are indicated in bold format.

are ca. 0.17 Å shorter than the other four bonds. It is clear that
the HOMO of the alternative electron occupation shows
mainly dx2−y2 character. The repulsion along the x and y axes
between the dx2−y2 HOMO of Mn and the px and py orbitals of
Oβ‑diketonato on the x and y axes, respectively, as can be seen in
the antibonding character of the HOMO in in Figure 5B, leads
to the elongation of the Mn−O bond lengths along the x and y
axes; see bond lengths 1−4 in Table 1. This result is known as a
compression Jahn−Teller distortion (elongation of the Mn−O
bond lengths along the x and y axes, or shortening of the
Mn−O bond lengths along the z axis).
Careful evaluation of the bonds in Table 1 show that for the
elongation Jahn−Teller distortion we have two long Mn−O bonds
along the z axis and two medium to short bonds, as well as two
short bonds in the xy plane. This asymmetric kind of distortion,
especially when more pronounced, is called orthorhombic distortion
and is consistent with Jahn−Teller behavior.14 The Jahn−Teller
theorem only predicts that distortion must occur for degenerate
states; it does not give any indication of what kind of geometrical
distortion will occur, or how large this distortion will be. Figure 6. ADF/OLYP molecular orbital energy-level diagram of the
We also observe from the bonds tabulated in Table 1 that the optimized structures of Mn(CH3COCHCOCH3)3, showing elonga-
Jahn−Teller distortion along the z axis is more pronounced tion (left) and compression (right) Jahn−Teller distortion. The d-
than in the xy plane. This is understandable, since the dz2 based orbitals of the Mn complex are indicated in red. Only the top
frontier MOs are shown. Arrows pointing up and downward represent
orbital protrudes further along the z axis than the dx2−y2 orbital
α- and β-electrons, respectively.
along the x and y axes. Consequently, there is a stronger
repulsion between the dz2 orbital of Mn, and the pz orbital of
Oβ‑diketonato along the z axis than the repulsion between the the ground state of both Mn(C6H5COCHCOC6H5)3 and
dx2−y2 orbital of Mn and the px and py orbitals of Oβ‑diketonato Mn(CF3COCHCOCF3)3 also have an elongation Jahn−Teller
along the x and y axes. distortion, with two bonds over 0.2 Å longer than the other four
The DFT calculated energy of the electronic state with alternative bonds. The population of the elongation Jahn−Teller distortion of
electron filling is 3.6 kJ mol−1 higher than the lowest-energy state. Mn(C6H5COCHCOC6H5)3 is 91%, explaining why the two
Using the Boltzmann equation (eq 1), we find that the population known crystal structures of Mn(C6H5COCHCOC6H5)3 both
of Mn(CH3COCHCOCH3)3 that will occur with an elongation show an elongation Jahn−Teller distortion.15,16
Jahn−Teller distortion is 79%, relative to the 21% population found The only crystal structure of MnIII(CF3COCHCOCF3)3
to have compression Jahn−Teller distortion. published to date, according to the author’s knowledge,17,18 also
showed an elongation Jahn−Teller distortion, as was expected
nj (Ej −Ei) from the DFT calculations in this study, which predicted a 81%
ln =−
ni kT (1) population of the elongation Jahn−Teller distortion. Structures of
MnII(CF3COCHCOCF3)3− are octahedral.19,20 This also was
nj = the number of atoms with energy Ej relative to the number expected, because MnII(CF3COCHCOCF3)3− is a high-spin d5
of atoms ni with energy Ei at temperature T, k = Boltzmann complex with five unpaired electrons: one electron in each orbital
constant. The ADF/OLYP results of this study thus show that of the eg orbital group, and one electron in each orbital of the t2g
Mn(CH3COCHCOCH3)3 exists mainly with an elongation Jahn− orbital group.
Teller distortion, although compression Jahn−Teller distortion is Lastly, it is important to evaluate whether the metal orbitals
also possible, as indeed has been observed experimentally.14 of the optimized structures of Mn(CH3COCHCOCH3)3
The bond lengths of the lowest energy DFT optimized structure indeed have the order as predicted in Figure 2. Figure 6 gives
of Mn(C6H5COCHCOC6H5)3 and Mn(CF3COCHCOCF3)3 are a molecular energy level diagram of the relative energies of
given in Table 1. As has been found for Mn(CH3COCHCOCH3)3, the molecular orbitals of the two optimized structures of
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Journal of Chemical Education
Mn(CH3COCHCOCH3)3, showing both elongation and
compression Jahn−Teller distortion. We observe that the
order of the energy levels is indeed as expected. First, the three d
orbitals of the t2g set, the dxy, dxz, and dyz orbitals, are more stable
(lower energy) than the dz2 or dx2−y2 orbitals, as would be
expected for a distorted octahedral ligand field. Second, the filled
dz2 orbital (HOMO) is lower in energy than the empty dx2−y2
orbital (LUMO) in the case of the elongation Jahn−Teller
distortion, and vice versa for the compression Jahn−Teller
distortion.
■
CONCLUSION
Summarizing, we have illustrated that DFT computational
chemical methods can serve as a simple but illustrative
representation, aiding the understanding of the Jahn−Teller
theorem. DFT provides a convenient way to predict the relative
geometric and energetic effect due to the JTE. DFT also
provides the method to calculate the opposite Jahn−Teller
distortion and to predict the population of each. The calculated
ratio of 79:21 for the elongation/compression Jahn−Teller
distortion for Mn(CH3COCHCOCH3)3 complexes explains
why both the compression and elongation Jahn−Teller
distortion is observed in solid state crystal structures.
■
ASSOCIATED CONTENT
*
S Supporting Information
[Optional, except for laboratories.] Student handouts, opti-
mized coordinates; example input files of the DFT calculations.
This material is available via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: conradj@ufs.ac.za.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work has received support from the South African
National Research Foundation and the Central Research Fund
of the University of the Free State, Bloemfontein.
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