Synthesis, characterization, and theoretical studies of metal complexes derived from the chiral tripyridyldiamine ligand Bn-CDPy3

Article abstract of DOI:10.1021/ic100322p

Synthesis and characterization of metal complexes of the chiral tripyridyldiamine ligand Bn-CDPy3 (1), derived from trans-1,2- diaminocyclohexane, are described, along with theoretical studies that support the experimental data. These studies confirm that

Full text of DOI:10.1021/ic100322p

5202 Inorg. Chem. 2010, 49, 5202–5211
DOI: 10.1021/ic100322p
Synthesis, Characterization, and Theoretical Studies of Metal Complexes Derived
from the Chiral Tripyridyldiamine Ligand Bn-CDPy3
Ahmed I. Abouelatta, Jason A. Sonk, Mirvat M. Hammoud, Danielle M. Zurcher, Joshua J. McKamie,
H. Bernhard Schlegel, and Jeremy J. Kodanko*
Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, Michigan 48202
Received February 17, 2010
Synthesis and characterization of metal complexes of the chiral tripyridyldiamine ligand Bn-CDPy3 (1), derived from
trans-1,2-diaminocyclohexane, are described, along with theoretical studies that support the experimental data. These
studies confirm that a single coordination geometry, out of five possible, is favored for octahedral complexes of the type
[M(Bn-CDPy3)Cl], where M equals Co(III), Fe(II), and Zn(II). A combination of X-ray crystallographic and NMR
spectroscopic methods was used to define the structures of the complexes [Co(Bn-CDPy3)Cl]Cl2 (5), [Fe(Bn-
CDPy3)Cl]X (X = FeCl4, Cl, ClO4, 6-8), and [Zn(Bn-CDPy3)Cl]2ZnCl4 (9) in the solid state and in solution.
Experimental and theoretical data indicate that the most stable coordination geometry for all complexes possesses the
Cl group trans to a basic amine donor and three pyridyl donors adopting the mer geometry, with two pyridyl N-donors
adopting a coplanar geometry with respect to the M-Cl bond and the third pyridyl donor perpendicular to that axis.
Calculations indicate that the ability to favor a single geometry is born from the chiral ligand, which prefers to be in a
single conformation in metal complexes due to steric interactions and electronic factors. Calculated structures of the
complexes were used to locate key interactions among the various diastereomeric complexes that are proposed to
create an energetic preference for the coordination geometry observed in the metal complexes of 1.
Introduction
binding mode has led the way to a variety of interesting
reactivities not easily accessed by other ligand types. In parti-
cular, these ligands have demonstrated the ability to stabilize
high-valent metal centers2,3 and block bimolecular decay pro-
cesses of reactive intermediates observed when using ligands of
lower denticity. Also important has been their ability to
participate in atom- or group-transfer reactions.4 Groups found
in the sixth position of such complexes have included oxo,5-9
The transfer of chirality from an asymmetric ligand to a
metal center has been a long-standing principle of coordina-
tion chemistry. Due to their ability to create an asymmetric
environment around the metal center, chiral ligands have
been used extensively in asymmetric synthesis and catalysis,
as well as supramolecular chemistry. The ability to predict
and control the coordination geometry of a ligand when
bound to a metal center is certainly an important aspect of
this chemistry, because the geometry can dictate the shape of
the molecule and the asymmetric environment around the
metal center.1 Chirality can be introduced into a ligand by
using building blocks that contain planar chiral or stereo-
genic centers. Of the various building blocks available, trans-
1,2-diaminocyclohexane has been common, serving as the
key chiral constituent in hundreds of asymmetric ligands.
Thus, this important chiral diamine can be considered a
privileged scaffold for ligand design.
(2) Que, L. Acc. Chem. Res. 2007, 40, 493–500.
(3) Nam, W. Acc. Chem. Res. 2007, 40, 522–531.
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Lopez de Laorden, C.; Mas-Balleste, R.; Merz, M.; Que, L., Jr. Angew.
Chem., Int. Ed. 2006, 45, 3446–3449.
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Cramer, C. J.; Que, L., Jr. Angew. Chem., Int. Ed. 2005, 44, 3690–3694.
(6) Kaizer, J.; Klinker, E. J.; Oh, N. Y.; Rohde, J.-U.; Song, W. J.;
€
Stubna, A.; Kim, J.; Munck, E.; Nam, W.; Que, L., Jr. J. Am. Chem. Soc.
2004, 126, 472–473.
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Halfen, J. A.; Muenck, E.; Nam, W.; Que, L., Jr. Science 2005, 310, 1000–
1002.
The coordination chemistry of nitrogen-rich pentadentate
ligands has received much attention (Figure 1). Pentadentate
ligands display the unique ability to coordinate to an octahe-
dral metal center with five donors, while leaving the sixth
position open for binding to an additional group. This special
(8) Sastri, C. V.; Park, M. J.; Ohta, T.; Jackson, T. A.; Stubna, A.; Seo,
M. S.; Lee, J.; Kim, J.; Kitagawa, T.; Muenck, E.; Que, L., Jr.; Nam, W.
J. Am. Chem. Soc. 2005, 127, 12494–12495.
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*To whom correspondence should be addressed. E-mail: jkodanko@
chem.wayne.edu.
(1) Knof, U.; Von Zelewsky, A. Angew. Chem., Int. Ed. 1999, 38, 303–322.
r
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Article
Inorganic Chemistry, Vol. 49, No. 11, 2010 5203
Figure 1. Examples of known pentadentate ligands containing multiple N-donors and their derivatives.
hydroperoxo,10-12 azide,13 imidio,14 nitrosyl,15 nitrido,16 cyanide,17
and halogens.17 Despite such attention, the element of chir-
ality has been noticeably absent in these ligands. In fact, there
are only a few examples of chiral pentadentate ligands
reported that contain similar nitrogen-rich donor sets.18-24
Considering there have been few reported examples of
ligands of this type, we initiated studies to define new chiral
pentadentate ligands with nitrogen-rich donor sets. To begin
our studies, we chose to merge the privileged scaffold trans-
1,2-diaminocyclohexane with the general structure of the
R-TPEN class of pentadentate ligands (Figure 1). In this
operation the ethyl bridge between the two basic amines of
the parent Bn-TPEN was replaced with a cyclohexyl linker,
yielding Bn-CDPy3 (Figure 2). While seemingly straightfor-
ward, the new cyclohexane motif added complexity and new
questions surrounding the coordination chemistry of the
chiral ligand. By differentiating the amines of the diamino-
cyclohexane backbone, the C2 symmetry of the ligand is
destroyed, creating a C1 symmetric ligand in its place. This
lowering of symmetry creates the opportunity for the ligand
to access more coordination modes than possible for tetra- or
Figure 2. Structure of (R,R)-Bn-CDPy3 (1), a chiral pentadentate
ligand.
hexadentate ligands derived from trans-1,2-diaminocyclo-
hexane that carry identical donors on the two amine
centers.25-28 Furthermore, the element of chirality conferred
by the cyclohexane linker would create the possibility for
additional stereoisomeric coordination modes; that is, modes
that were equivalent or enantiomeric in the case of the
R-TPEN ligands would become diastereomeric in the case
of the new chiral ligand. In this full paper, we expand on our
initial studies that described the characterization of the
29
complex [Co(Bn-CDPy3)Cl]Cl2 and report that a single
coordination geometry is preferred from five possible modes
for transition metal complexes derived from the chiral
pentadentate ligand Bn-CDPy3. In addition, we report
theoretical studies that support these experimental observa-
tions, as well as molecular modeling studies that shed light on
the origin of the remarkable control over coordination
geometry that is observed with the asymmetric ligand Bn-
CDPy3.
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Experimental Section
Instrumentation. All reagents were purchased from commer-
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on a Varian FT-NMR Unity-300, Mercury-400, or Oxford-500
MHz spectrometer. Mass spectra were recorded on a Waters
ZQ2000 single quadrupole mass spectrometer using an electro-
spray ionization source. IR spectra were recorded on a Nicolet
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5204 Inorganic Chemistry, Vol. 49, No. 11, 2010
Abouelatta et al.
FT-IR spectrophotometer. UV-vis spectra were recorded on a
Varian Cary 50 spectrophotometer. CD spectral data were
recorded on a Chirascan circular dichroism spectrophotometer.
Reactions were performed under ambient atmosphere. Oxygen-
and moisture-sensitive reactions were performed inside an
MBraun Labmaster 130 glovebox. Molecular modeling studies
were performed with the program MacPyMol.
cc-pVTZ basis set. The reference in the NMR spectrum was TMS
(tetramethylsilane) calculated usingthe same functional andbasis
set. Calculations of the UV-vis spectra utilized time-dependent
density functional theory (TD-DFT)44-50 with the long-range
corrected LC-ωPBE functional51-54 and the cc-pVTZ basis set.
All calculations were performed using the development version of
the Gaussian software suite.55 Overlap studies with calculated
structures were performed with MacPyMOL (see Supporting
Information).
Computational Details. All five isomers of the cobalt-, zinc-,
and iron-containing structures were fully optimized using the
TPSS pure functional30 with an all-electron cc-pVTZ basis
set31-35 on the ligands and metals. Equilibrium geometries were
confirmed using vibrational frequency analysis. For compar-
ison, optimizations where also carried out with the B3LYP
hybrid functional.36-38 Single-point calculations were per-
formed on the optimized structure of the ligand without the
metal halide using the TPSS pure density functional with the
cc-pVTZ basis set. NBO39 analysis was used to look at the nature
of the molecular orbitals of the calculated structures. NMR
calculations were performed using the gauge-independent atomic
orbital (GIAO) method40-43 with the TPSS functional and the
X-ray Crystallography. Diffraction data were measured on a
Bruker X8 APEX-II kappa geometry diffractometer with Mo
radiation and a graphite monochromator. Frames were col-
lected at 100 K with the detector at 40 mm and 0.3 degrees
between each frame and were recorded for 10 s. APEX-II56
and SHELX57 software were used in the collection and refine-
ment of the models.
Crystals of [Co(Bn-CDPy3)Cl]Cl2 (5) appeared as violet
plates; 92 682 reflections were measured, yielding 17 503 unique
data (Rint = 0.052). Hydrogen atoms in the complex were placed
in calculated positions. The asymmetric unit contains two
independent Co complexes and a solvent region consisting of
four chloride ions, six water solvates, and one ethanol molecule.
Of these, the ethanol and one water molecule were highly
disordered, lying near the inversion center, and a reasonable
chemical refinement was not possible. Spek’s PLATON pro-
gram was employed to account for approximately 66 e- via
SQUEEZE.58 The highest ΔF peak (∼2 e-) was located in the
vicinity of the disordered solvent.
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Crystals of [Fe(Bn-CDPy3)Cl]ClO4 (8) were yellow and irre-
gular fragments. 69 185 points were integrated and merged into
13 686 independent data with Rint = 0.0343. Hydrogen atoms
were placed in calculated positions. The asymmetric unit contains
one Fe complex, one perchlorate counter ion, one equivalent of
acetonitrile and one disordered equivalent of diethyl ether. The
diethyl ether disorder was handled by assigning two sets of
positions and holding these partial occupancy positions isotropic
during refinement with their bond distances fixed. The highest
difference map peaks (1-1.4 e-) were in the vicinity of this
disordered solvate.
(R,R)-N1-Benzyl-N1,N2,N2-tris(pyridin-2-ylmethyl)cyclohexane-
1,2-diamine (Bn-CDPy3, 1). Enantioenriched 1 was synthesized
according to the reported procedure starting from the enan-
tioenriched starting material (1R,2R)-(-)-1,2-cyclohexane-
diamine (99% ee).29 1H and 13C NMR and mass spectral
data for enantioenriched 1 matched data for the racemic
compound. [R]D = 51.1 (c 1.0, MeOH).
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[Co(Bn-CDPy3)Cl]Cl2 (5 5H2O). The cobalt(III) complex
3
[Co(Bn-CDPy3)Cl]Cl2 5H2O was prepared according to literature
3
1
using the enantiopure (R,R)-Bn-CDPy3, 1.29 Mass, H and 13C
NMR, and UV-vis spectral data matched with a racemic complex.
[Fe(Bn-CDPy3)Cl]Cl (7). A solution of ligand 1 (0.20 g, 0.418
mmol) in DCM (12 mL) was stirred with FeCl2 (0.053 g, 0.418
mmol) inside the glovebox for 4 h, resulting in the formation of a
yellow solution. The solution was filtered and concentrated
inside the glovebox. The resultant golden yellow solid was
recrystallized by vapor diffusion from MeCN/Et2O inside the
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G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.;
Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.;
Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.;
Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.;
Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V.;
Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.;
Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.;
Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts,
R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.;
Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth,
G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Parandekar, P. V.;
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glovebox, yielding yellow needle crystals of 7 3H2O (0.16 g,
3
63%). Mp = 155-156 °C; χmol = 4.90 μB. 1H NMR (CD3OD):
δ 160.2, 140.5, 108.4, 99.1, 96.4, 89.1, 57.4, 56.6, 52.4, 49.5, 41.6,
40.0, 26.1, 24.4, 19.2, 15.4, 11.5, 9.4, 7.5, 4.5, 3.0, 2.5, 1.9, 1.7, 1.3,
-0.8, -7.4, -21.3, -24.5. IR (thin film): 3411(s), 3060(w),
3027(w), 2933(s), 2860(m), 2359(w), 1602(s), 1570(m), 1482(s),
1443(s), 1384(w), 1352(w), 1316(w), 1296(w), 1245(w), 1204(m),
1155(m), 1099(m), 1077(m), 1052(m), 1016(m), 978(w), 960(w),
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Madison WI, 2009.
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Article
Inorganic Chemistry, Vol. 49, No. 11, 2010 5205
931(w), 884(w), 816(w), 758(s), 708(s) cm-1. Anal. Calcd for
C31H41Cl2FeN5O3 (3 3H2O): C, 56.55; H, 6.28; N, 10.64.
Found: C, 56.44; H, 5.89; N, 10.67.
Scheme 1. Synthesis of Bn-CDPy3 (1)
3
[Fe(Bn-CDPy3)Cl]ClO4 (8). The complex [Fe(Bn-CDPy3)-
Cl]ClO4 (4) was obtained by ion exchange of [Fe(Bn-CDPy3)-
Cl]Cl (7) and AgClO4. A stock solution of AgClO4 (0.0365 g,
0.175 mmol) in MeCN (2.5 mL) was prepared in the glovebox.
The complex [Fe(Bn-CDPy3)Cl]Cl (7) (0.02 g, 0.035 mmol) was
dissolved in MeCN (0.5 mL), mixed with 0.5 mL of the prepared
AgClO4 solution, and stirred for 5 min, resulting in formation of
a white precipitate (AgCl). The precipitate was removed by
filtration, and [Fe(Bn-CDPy3)Cl]ClO4 was crystallized by vapor
diffusion with 3 mL of Et2O, yielding yellow crystals of 8 H2O
3
(10 mg, 34%). These crystals were subjected to X-ray crystal-
lographic analysis. Mp = 146-148 °C. IR (thin film): 3409(s),
3065(w), 2936(m), 2860(w), 1657(m), 1604(m), 1482(w), 1444(m),
1142(s), 1109(s), 1090(s), 1017(w), 763(m), 708(w), 661(w), 625(m)
cm-1. Anal. Calcd for C31H37Cl2FeN5O5 (4 H2O): C, 54.24; H,
3
5.43; N; 10.20. Found: C, 54.20; H, 5.35; N, 10.34.
[Zn(Bn-CDPy3)Cl]2ZnCl4 (9). The ligand (R,R)-Bn-CDPy3
(0.20 g, 0.418 mmol) was dissolved in THF (5 mL) and stirred
with ZnCl2 (0.085 g, 0.627 mmol) inside the glovebox overnight.
A white precipitate formed immediately and then disappeared
upon stirring. The solution was concentrated inside the glove-
box. The resultant lightly colored solid was stirred with ether
overnight in the glovebox. The suspension was filtered, and the
colorless solid was dried in vacuo then outside the glovebox in a
Shlenk tube at 120 °C overnight to remove traces of THF,
yielding a colorless solid (0.27 g, 47%). Mp =190 °C (dec). 1H
NMR (CD3OD): δ 9.24 (d, J = 4.9 Hz, 1H), 8.84 (d, J = 4.9 Hz,
1H), 8.02 (m, 1H), 7.93 (m, 1H), 7.80 (m, 1H), 7.72 (d, J = 4.9 Hz,
1H), 7.59 (d, J = 8.1 Hz, 1H), 7.49 (m, 3H), 7.37 (m, 7 H), 4.82 (d,
J = 17.8 Hz, 1H), 4.70 (d, J = 15.4 Hz, 1H), 4.58 (d, J = 13.8 Hz,
1H), 4.37 (d, J = 16.2 Hz, 1H), 4.20 (d, J = 15.4 Hz, 1H), 3.94 (d,
J = 17.0 Hz, 2H), 3.47 (d, J = 13.8 Hz, 1H), 3.28 (m, 1H), 2.04 (d,
J = 13.0 Hz, 1H), 1.91 (dt, J = 11.4, 3.2 Hz, 1H), 1.69 (d, J = 17
Hz, 1H), 1.60 (dt, J = 12.2, 3.2 Hz, 1H), 1.45 (d, J = 12.2 Hz, 1H),
1.19 (m, 2H), 0.98 (m, 1H), 0.87 (m, 1H). 13C NMR (CD3OD): δ
155.8, 155.7, 154.5, 148.1, 147.8, 145.9, 140.6, 140.4, 139.7, 134.6,
130.7, 128.6, 125.3, 124.6, 124.5, 123.9, 123.6, 123.5, 68.8, 64.0,
62.8, 62.5, 54.5, 53.7, 29.2, 26.1, 24.6, 24.5. IR (thin film): 3466(s),
3061(w), 2938(m), 2861(w), 2281(w), 1604(s), 1574(m), 1484(m),
1443(s), 1384(w), 1315(w), 1295(w), 1204(w), 1156(w), 1101(w),
1084(w), 1053(m), 1019(m), 978(w), 934(w), 885(w), 853(w),
763(s), 708(m) cm-1. Anal. Calcd for C62H72Cl6N10OZn3C
Scheme 2. Synthesis of Bn-CDPy3 Metal Complexesa
a (a) trans-[Co(Py)4Cl2]Cl 6H2O, CH2Cl2, 12 h, dark, 79%. (b) FeCl2,
DCM, 4 h, 63%. (c) AgClO4, MeCN, 34%. (d) ZnCl2, THF, 47%.
3
starting from racemic trans-1,2-diaminocyclohexane, and
in enantioenriched form, starting from the enantioen-
riched ligand (1R,2R)-(-)-1,2-cyclohexanediamine (99% ee).
X-ray crystallographic studies were carried out with
racemic ligand 1 in order to facilitate the crystallization
process (metal complexes crystallized as racemates in the
achiral space group P1, vide infra), and complexes derived
from the enantioenriched 1 were used for CD studies.
Cobalt, zinc, and iron metal complexes derived from 1
were synthesized (Scheme 2). The Co(III) complex was
prepared by treating the ligand 1 with 1 equiv of trans-[Co-
(5 H2O): C, 53.87; H, 5.25; N, 10.13. Found: C, 53.81; H, 5.08;
3
N, 9.91.59 LRMS (ESMS): 576.2 (ZnBn-CDPy3Cl).
Results
(Py)4Cl2]Cl 6H2O in CH2Cl2 in the dark. After 12 h a
3
purple solid was isolated that contained the complex
[Co(Bn-CDPy3)Cl]Cl2 (5) as a mixture of stereoisomers,
with the one isomer major, one minor (5:1 major:minor)
and trace amounts of other isomers. Recrystallization of
the purple solid using EtOH with Et2O vapor diffusion
enriched the sample and gave purple plates of 5 as a >10:1
Synthesis. Synthesis of the ligand Bn-CDPy3 began
from the dipyridyldiamine 2, which is available in two
steps from the commercially available starting material
trans-1,2-diaminocyclohexane.29 Treatment of 2 with one
equivalent of 2-pyridinecarboxaldehyde in the presence
˚
of 4 A molecular sieves gave aminal 3, a stable compound
1
mixture of major to minor isomers, as evidenced by H
NMR analysis. The reaction of 1 in CH2Cl2 with 1 equiv
of FeCl3 6H2O in EtOH produced a complex mixture
that was isolable by alumina chromatography, in 88%
yield. Reduction of the aminal using NaBH3CN and TFA
gave the tripyridyldiamine 4 in 96% yield, which was
alkylated with BnBr to give Bn-CDPy3 in 99% yield and
84% overall yield from 2. The late stage introduction of
the benzyl group during the synthesis of 1 was ideal,
because analogues of 1 with different R-groups can be
prepared readily from 4. For the studies presented herein,
it was necessary to prepare the ligand in racemic form,
3
of products. Trace amounts of the complex [Fe(Bn-
CDPy3)Cl](FeCl4) (6) were obtained from this reaction
and were identified by X-ray crystallographic analysis (see
Supporting Information for structure). Attempts to obtain
preparative amounts of 6 and a satisfactory elemental
analysis of the material were unsuccessful. Therefore, an
alternative synthesis of an Fe(II) complex was devised.
Reaction of 1 with 1 equiv of FeCl2 in CH2Cl2, followed
by recrystallization from MeCN with Et2O vapor diffusion,
(59) Jackson, W. G.; Sargeson, A. M.; Tucker, P. A.; Watson, A. D.
J. Am. Chem. Soc. 1981, 103, 533–540.

5206 Inorganic Chemistry, Vol. 49, No. 11, 2010
Abouelatta et al.
˚
Table 1. X-ray Crystallographic Data for 5 and 8
Table 2. Selected Bond Lengths (A) for 5 and 8
[Co(Bn-CDPy3)Cl]Cl2
(5)
[Fe(Bn-CDPy3)Cl]ClO4
(8)
[Co(Bn-
CDPy3)Cl]Cl2 (5)
[Fe(Bn-
CDPy3)Cl]ClO4 (8)
parameter
bond
bond
empirical
formula
fw
C
32H44Cl3Co1N5O3.5
C37H48Cl2FeN6O5
Co(1)-N(1)
Co(1)-N(2)
Co(1)-N(3)
Co(1)-N(4)
Co(1)-N(5)
Co(1)-Cl(1)
1.961(2)
2.016(2)
1.939(3)
1.954(3)
1.946(3)
2.241(1)
Fe(1)-N(1)
Fe(1)-N(2)
Fe(1)-N(3)
Fe(1)-N(4)
Fe(1)-N(5)
Fe(1)-Cl(1)
2.236(1)
2.268(1)
2.163(1)
2.202(1)
2.182(1)
2.3390(4)
720.00
triclinic
P1
783.56
triclinic
P1
cryst syst
space group
˚
a (A)
14.5658(3)
14.8438(3)
18.4793(4)
107.3480(1)
105.8420(1)
96.4300(1)
3586.6(1)
4
R1 = 0.0457,
wR2 = 0.1222
R1 = 0.0642,
wR2 = 0.1296
9.4228(3)
15.1824(5)
15.2967(8)
114.517(2)
97.436(2)
102.973(2)
1878.1(1)
2
R1 = 0.0509,
wR2 = 0.1421
R1 = 0.0614,
wR2 = 0.1489
˚
b (A)
Supporting Information for 6). The FeII complex 8
crystallizes as a racemate in the triclinic space group P1,
with Z = 2. The iron center contains a N5Cl donor atom
set in which mer geometry is adopted by the three pyridyl
donors. The coordination environment of the ferrous
center shows a slightly distorted octahedral geometry
with bond angles ranging from 78.32(5)° to 104.09(4)°.
˚
c (A)
R (deg)
β (deg)
γ (deg)
3
˚
V (A )
Z
final R indices
[I > 2σ(I)]
R indices
(all data)
˚
For 8, the Fe(1)-N(1) bond length at 2.236(1) A is
significantly shorter than the Fe(1)-N(2) bond length
of 2.268(1) A. Bond lengths between the pyridyl donors
˚
gave the iron complex [Fe(Bn-CDPy3)Cl](Cl) (7) as a
microcrystalline yellow solid in 63% yield. Because this
material was not suitable for X-ray crystallographic analy-
sis, the iron complex [Fe(Bn-CDPy3)Cl](ClO4) (8) was
prepared by ion exchange of 7 with 1 equiv of AgClO4 in
MeCN. Crystalsof8suitableforX-rayanalysisweregrown
from MeCN with Et2O vapor diffusion. Reaction of the
ligand 1 with 1.5 equiv of ZnCl2 in THF produced the
complex [Zn(Bn-CDPy3)Cl]2ZnCl4 (9), which was ob-
tained as a colorless solid in 47% yield after washing with
Et2O.
X-ray Crystallographic Studies. X-ray crystallographic
data for compounds 5 and 8 (see Supporting Information
for 6) and the parameters of data collections are described
in Table 1. Tables 2 and 3 list selected bond lengths and
bond angles, respectively.
and the iron centers, Fe(1)-N(3), Fe(1)-N(4), and Fe-
˚
(1)-N(5), are 2.163(1), 2.202(1), and 2.182(1) A, respec-
tively. Bond lengths to the iron center in 8 are in good
agreement with [Fe-N5]average distances of the paramag-
netic [FeII(Bn-Tpen)X] complexes, indicating that the
complexes contain a high-spin (S = 2) Fe(II) ion.60 The
˚
Fe(1)-Cl(1) bond length for 8 is 2.3390(4) A.
Spectroscopic Studies
1
NMR Spectroscopy. H NMR spectroscopic data for
compounds 5, 7, and 9 revealed a distinct pattern for the
pyridyl C-H resonances, consistent with the compounds
adopting the same conformation in solution. Resonances
observed in the 1H NMR spectrum of the Co(III) complex
5 in CD3OD lie between 9.70 and 1.08 ppm, confirming
the compound is a low-spin diamagnetic complex. An
The Co(III) complex 5 crystallizes as a racemate in the
triclinic space group P1, with Z = 4. Two enantiomeric
dications of [Co(Bn-CDPy3)Cl]2þ that are nearly identi-
cal in structure are located in the asymmetric unit in
addition to four chloride anions, consistent with the
complex bearing a Co(III) center. Due to their similarity,
structural parameters for only one of the dications are
described herein; parameters for the second dication can
be found in the Supporting Information. The cobalt
center has a mixed N and Cl (N5Cl) donor atom set in
which mer geometry is adopted by the three pyridine
donors (Figure 3). The coordination environment around
the metal center possesses a slightly distorted octahedral
geometry, with bond angles ranging from 84.09(8)° to
97.19(7)°. The basic amine N-donor N(1) has a signifi-
1
expansion of the aromatic region of the H NMR spec-
trum of 5 is shown in Figure 5a. In this spectrum, two
resonances corresponding to the protons found on the
2-position of the pyridine rings are shifted downfield to
9.70 and 9.04 ppm, while the third 2-pyridyl C-H reso-
nance is shifted upfield to 7.34 ppm (see red arrows). This
assignment agrees well with calculated data and also with
literature precedence (vide infra).5 A similar pattern was
1
observed in the H NMR spectrum of the diamagnetic
Zn(II) complex 9 (Figure 5b), with resonances located at
9.24, 8.84, and 7.72 ppm, consistent with 9 adopting a
similar conformation to 5. The complex [Fe(Bn-CDPy3)-
Cl]Cl (7) showed a paramagnetically shifted and relatively
sharp 1H NMR spectrum, with resonances ranging from
-25 to 160 ppm (Figure 5c). The high-spin nature of 7 was
confirmed in the solid state with molar susceptibility of
4.90 μB, which agrees well for a S = 2 Fe(II) compound.
˚
cantly shorter bond length to Co(1), measuring 1.961(2) A,
˚
than the Co(1)-N(2) distance of 2.016(2) A. Bond lengths
Co(1)-N(3), Co(1)-N(4), and Co(1)-N(5) are nearly
identical, at 1.939(3), 1.954(3), and 1.946(3) A, respec-
1
Resonances in the H NMR spectrum of 7 that were
˚
broad and located the furthest downfield were assigned to
the 2-pyridyl C-H protons based on precedence.61 Inter-
estingly, the same pattern is evident in the paramagnetic
1H NMR spectrum of 7 as was observed for the diamag-
netic compounds 5 and 7. Namely, two protons are
˚
tively. The Co(1)-Cl(1) bond length is 2.241(1) A. All
the bond lengths are consistent with the dication of
[Co(Bn-CDPy3)Cl]2þ containing a low-spin Co(III) me-
tal center.29
Crystallographic data for complexes 6 and 8 revealed
that the [Fe(Bn-CDPy3)Cl]þ cation adopts a solid-state
conformation that is nearly identical between the two
compounds, with little influence from the tetrachlorofer-
rate or perchlorate counteranion (see Figure 4 for 8 and
(60) Bernal, I.; Jensen, I. M.; Jensen, K. B.; McKenzie, C. J.; Toftlund, H.;
Tuchagues, J.-P. J. Chem. Soc., Dalton Trans. 1995, 3667–3675.
(61) Britovsek, G. J. P.; England, J.; White, A. J. P. Inorg. Chem. 2005, 44,
8125–8134.

Article
Inorganic Chemistry, Vol. 49, No. 11, 2010 5207
Table 3. Selected Bond Angles (deg) for 5 and 8
bond angle
[Co(Bn-CDPy3)Cl]Cl2 (5)
bond angle
[Fe(Bn-CDPy3)Cl]ClO4 (8)
N(1)-Co(1)-Cl(1)
N(2)-Co(1)-Cl(1)
N(3)-Co(1)-Cl(1)
N(4)-Co(1)-Cl(1)
N(5)-Co(1)-Cl(1)
N(1)-Co(1)-N(2)
N(3)-Co(1)-N(1)
N(3)-Co(1)-N(2)
N(3)-Co(1)-N(4)
N(3)-Co(1)-N(5)
N(4)-Co(1)-N(1)
N(4)-Co(1)-N(2)
N(5)-Co(1)-N(1)
N(5)-Co(1)-N(2)
N(5)-Co(1)-N(4)
178.83(6)
94.34(5)
94.74(6)
94.18(6)
85.39(6)
86.80(7)
84.11(8)
170.58(8)
84.63(8)
94.16(8)
85.90(8)
97.19(7)
94.50(8)
84.09(8)
178.68(8)
N(1)-Fe(1)-Cl(1)
N(2)-Fe(1)-Cl(1)
N(3)-Fe(1)-Cl(1)
N(4)-Fe(1)-Cl(1)
N(5)-Fe(1)-Cl(1)
N(1)-Fe(1)-N(2)
N(4)-Fe(1)-N(1)
N(4)-Fe(1)-N(2)
N(3)-Fe(1)-N(1)
N(3)-Fe(1)-N(4)
N(3)-Fe(1)-N(2)
N(3)-Fe(1)-N(5)
N(5)-Fe(1)-N(1)
N(5)-Fe(1)-N(4)
N(5)-Fe(1)-N(2)
172.08(4)
100.32(4)
104.09(4)
94.43(4)
95.28(4)
78.39(5)
78.32(5)
102.43(5)
78.32(5)
82.34(5)
154.70(5)
94.69(5)
92.01(5)
170.26(5)
76.39(5)
spin systems in 9, and NOESY data were used to identify
close contacts between protons through space. Key pro-
tons used in the structural assignment are indicated in
Figure 6; a full assignment of all protons is located in the
Supporting Information. Analysis of HMQC data indi-
cated that the two methine protons of the cyclohexyl ring,
H(6) and H(1), were located at 1.91 and 3.28 ppm,
respectively, in the 1H NMR spectrum of 9. The methy-
lene proton H(13B) showed strong cross-peaks with H(6)
and H(2B) in the NOESY spectrum, consistent with this
proton lying between the two axial protons, a key struc-
tural feature of the preferred coordination geometry
(vide infra). The pyridyl proton H(21) was assigned
according to COSY data, which indicated that the proton
H(24), assigned as the resonance furthest upfield in the 1H
NMR spectrum at 7.72 ppm, was in the same ring as
H(21). This proton showed a strong cross-peak in the
NOESY spectrum with H(19A), which was connected to
H(5A), to H(1), and finally to H(7A).
Figure 3. ORTEP diagram of the dication [Co(Bn-CDPy3)Cl]2þ from
compound5. Thermal ellipsoidsare shown at 50% probability. Hydrogen
atoms are omitted for clarity.
UV-Vis Spectroscopy. The Fe(II) complex 7 dissolved
in MeOH to form a yellow solution. The UV-vis absorp-
tion spectra of complex 7 showed two absorbances with
λmax at 413 and 362 nm, with ε = 1910 and 1790 M-1
cm-1, respectively (Figure 7). The intensities of these
bands are in good agreement with data for similar high-
spin Fe(II) complexes, which agrees well with the para-
magnetic shifts observed in 1H NMR spectrum obtained
for 7 in CD3OD, as well as the solid-state magnetic
susceptibility data.62 The Co(III) complex 5 gives a purple
solution with an absorption maximum at λmax = 555 nm,
ε = 159 M-1 cm-1 with a shoulder at 388 nm (Figure 7).
CD Spectroscopy. CD spectroscopic analysis of the
chiral pentadentate ligand (R,R)-Bn-CDPy3 (1) and the
Zn(II) complex 9 revealed no CD activity in the range
200-800 nm. On the other hand, both the Co(III) com-
plex 5 and the Fe(II) complex 7 showed Cotton effects
(Figure 8). In the case of the enantioenriched Co(III)
complex 5, two major features were observed in the CD
spectrum. A positive maximum is located at 415 nm,
along with a bisignate couplet centered at the maximum
absorbance of 5 (550 nm), characteristic of exciton split-
ting. In contrast, complex 7 showed a negative maximum
at 508 nm, with no exciton coupling.
Figure 4. ORTEP diagram of the cation [Fe(Bn-CDPy3)Cl]þ from 8.
Thermal ellipsoids are shown at 50% probability. Hydrogen atoms are
omitted for clarity.
located downfield at 160 and 141 ppm, while the third is
upfield at 89 ppm.
Because X-ray crystallographic data for the Zn(II)
complex 9 were not available, additional NMR data were
acquired in order to support the structural assignment of
9. A combination of COSY, DEPT, and HMQC experi-
ments were used to define protons and carbons in isolated
(62) Ortega-Villar, N.; Ugalde-Saldivar, V. M.; Munoz, M. C.; Ortiz-Frade,
L. A.; Alvarado-Rodriguez, J. G.; Real, J. A.; Moreno-Esparza, R. Inorg.
Chem. 2007, 46, 7285–7293.

5208 Inorganic Chemistry, Vol. 49, No. 11, 2010
Abouelatta et al.
Figure 5. Expansions of 1H NMR spectra of [Co(Bn-CDPy3)Cl]Cl2 (5, spectrum a), [Zn(Bn-CDPy3)Cl]2ZnCl4 (9, spectrum b), and [Fe(Bn-CDPy3)Cl]Cl
(7, spectrum c) in CD3OD. A distinct pattern of two downfield and one upfield resonance (labeled with red arrows) was observed for the 2-pyridyl C-H
protons of compounds 5, 7, and 9. A minor amount of an unknown stereoisomer is present in the sample of 5. Full spectra can be found in the Supporting
Information.
Figure 7. UV-vis spectra of 5 (blue line) and 7 (red, dotted line) in
MeOH.
Figure 6. Three-dimensional models of [Zn(Bn-CDPy3)Cl]þ with most
hydrogen atoms omitted for clarity. Select hydrogen atoms showing NOE
contacts are labeled with intensities of strong (s) or weak (w). Models are
based on the calculated structure for [Zn(Bn-CDPy3)Cl]þ (vide infra). See
Supporting Information for further details.
Calculated Structures and Energetics
As shown in Figure 9, five isomers can be constructed for
M(Bn-CDPy3)Cl. The calculated relative energies are sum-
marized in Table 4 for M = Co(III), Fe(II), and Zn(II).
Results for the B3LYP calculations are available in the
Figure 8. CD spectra of 5 (blue line) and 7 (red, dotted line) in MeOH.
Supporting Information. For all of the complexes consid-
ered, the calculations predict isomer C to be the lowest
energy, in good agreement with the X-ray crystallographic
data for Co(III) and Fe(II) complexes and the NMR data for
the Zn(II) complex. The metal-ligand bond lengths and
angles are collected in the Supporting Information and
compare very well with the available experimental structural
data. For isomer C the rmsd for the heavy atoms in the crystal
the d10 Zn(II) complex. In three of the five isomers of the
M(Bn-CDPy3)Cl complexes, thepyridyl donors are arranged
meridionally (isomers A, B, and C) and two are facial
(isomers D and E). Isomer C is calculated to be the most
stable. If it was not for the cyclohexane ring, isomer A would
be the mirror image of isomer C and is the next most stable
isomer. For each of the metals considered, isomer B is ca. 8
kcal/mol less stable than C. In B, the two pyridyl rings are
trans to each other and are nearly coplanar, whereas none of
the pyridyl rings in isomers A and C lie in the same plane. The
two facial isomers, D and E, are 10-16 kcal/mol less stable
than C. Isomers D and E have the two pyridyl rings coplanar
and cis to each other.
˚
structure versus calculated structure is 0.182 A for the Co(III)
˚
complex and 0.139 A for the Fe(II) complex. The bond
6
˚
lengths for the d Co(III) complex are 0.2-0.3 A shorter
than for the Fe(II) and the Zn(II) complexes. This is in
keeping with the fact that the dz2 and dx2-y2 orbitals are
unoccupied in the low-spin d6 Co(III) complex, but are singly
and doubly occupied in the high-spin d5 Fe(II) complex and

Article
Inorganic Chemistry, Vol. 49, No. 11, 2010 5209
Figure 9. Isomers of M(Bn-CDPy3)Cl determined from calculations: A, B, and C display mer orientations of the pyridyl donors; D and E are fac.
Table 4. Relative Energies of the Five Isomers of [Co(Bn-CDPy3)Cl]2þ, [Zn(Bn-
Table 5. Comparison of X-ray Crystallographic Data and Calculated Structures
CDPy3)Cl]þ, and [Fe(Bn-CDPy3)Cl]þ in kcal/mol
for the [Co(Bn-CDPy3)Cl]2þ
,
[Zn(Bn-CDPy3)Cl]þ, and [Fe(Bn-CDPy3)Cl]þ
Cationsa
entire
complexa
ligand
onlyb
ligand-metal
isomer
interactionc
crystallographic isomer isomer isomer isomer isomer
D
data
C
A
B
E
C
Co
Zn
Fe
A
Co
Zn
Fe
B
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Co
M-Cl
M-N1
M-N2
M-N3
M-N4
M-N5
Zn
2.241(1)
1.962(2)
2.015(2)
1.941(2)
1.952(2)
1.945(2)
2.244
1.989
2.044
1.966
1.971
1.970
2.243
1.999
2.049
1.989
1.957
2.007
2.254
1.971
2.056
1.961
1.983
1.954
2.248
1.976
2.053
1.983
1.996
1.949
2.279
1.987
2.036
1.973
2.010
1.988
7.12
2.49
2.79
2.65
0.86
0.96
4.47
1.63
1.83
Co
Zn
Fe
D
Co
Zn
Fe
E
7.79
7.76
8.34
3.79
3.25
3.26
4.00
4.51
5.08
M-Cl
M-N1
M-N2
M-N3
M-N4
M-N5
Fe
M-Cl
M-N1
M-N2
M-N3
M-N4
M-N5
2.283
2.331
2.269
2.175
2.220
2.242
2.276
2.341
2.252
2.228
2.141
2.361
2.290
2.217
2.455
2.227
2.275
2.109
2.297
2.216
2.314
2.242
2.419
2.125
2.362
2.247
2.286
2.268
2.215
2.165
15.73
12.44
13.12
5.70
2.73
3.29
10.04
9.71
9.83
2.339(1)
2.236(1)
2.268(1)
2.163(1)
2.202(1)
2.182(1)
2.269
2.307
2.308
2.144
2.184
2.222
2.267
2.319
2.298
2.213
2.124
2.284
2.270
2.245
2.435
2.218
2.233
2.104
2.282
2.246
2.311
2.260
2.316
2.145
2.340
2.257
2.304
2.240
2.213
2.187
Co
Zn
Fe
13.45
12.44
12.41
3.15
2.73
2.79
10.31
9.71
9.62
a Energy of the M(Bn-CDPy3)Cl complex relative to isomer C.
b Single-point energies of the complexes with the metal chloride re-
moved, relative to isomer C; these energies reflect the differences in
the ligand distortion energies in the various isomers relative to isomer C;
the ligand distortion energies for isomer C are 20.64 and 1.08 kcal/mol
greater for the Co and Fe complexes than for the Zn complex. c Entire
complex energies minus the ligand-only energies; these energies reflect
the differences in the electronic interaction between the ligands and the
metal chlorides.
a
˚
Bond lengths in A and bond angles in deg; for atom numbering see
Figure 9. For isomer C, the rmsd for the heavy atoms in the crystal
2þ
˚
structure versus calculated structureþis 0.182 A for [Co(Bn-CDPy3)Cl]
˚
and 0.139 A for [Fe(Bn-CDPy3)Cl] .
electronic contribution for the mer isomers A-C is 5-10
kcal/mol more stabilizing than for the fac isomers, D and E.
There is a delicate balance between the numerous factors in
the electronic contribution, and it is not possible to single out
one dominant term either by looking at the NBO analysis or
by examining the geometric parameters. However, inspection
of the structures provides evidence for the trans effect63-65
and for interactions of the metal-ligand bonds with the π
system of the pyridyl rings. For example, metal-pyridyl
bonds trans to an amine nitrogen in isomers A-C are always
shorter than the metal-pyridyl bonds cis to the amine (see
Table 2). The Fe-N and Zn-N bonds trans to Cl are longer
than the corresponding bonds cis to Cl (for low-spin d6
Co(III), other factors contribute and the trans lengthening
by Cl is not evident). Interactions of the pyridyl π orbitals
with the metal-ligand antibonding orbitals are most clearly
seen in the fac isomers. The M-N bonds aligned with the π
Both steric ligand distortion and ligand-metal binding
energies contribute to the energy differences between the
various isomers. The ligand distortion contributions are
easily factored out by removing the metal chloride from the
complex and computing the energy of the ligand frozen at the
geometry of the complex. As shown in Table 4, the ligand of
isomer C has the lowest distortion energy for each metal
considered. Because of the shorter metal ligand bond dis-
tances, the ligand in the Co(III) complex C is 20 kcal/mol
more strained than the ligand in the corresponding Fe and Zn
complexes. For a given metal, the ligand of isomer A has the
next lowest distortion energy, and those for the remaining
isomers are 3-6 kcal/mol greater than for isomer C. The
distortion energies of the ligands in the facial isomers D and E
are not significantly higher than for the meridinal isomers
A-C.
˚
orbital of the pyridyl trans to the Cl (e.g., R(Zn-N4) 2.215 A
and R(Zn-N2) 2.286 A for Zn isomer E) are longer than the
˚
If the difference in the ligand distortion energy is sub-
tracted from the relative energy of the isomers, one is left
with differences in the electronic contribution arising from
the metal-ligand interactions. As indicated in Table 4, the
(63) Burdett, J. K.; Albright, T. A. Inorg. Chem. 1979, 18, 2112–2120.
(64) Coe, B. J.; Glenwright, S. J. Coord. Chem. Rev. 2000, 203, 5–80.
(65) Anderson, K. M.; Orpen, A. G. Chem. Commun. 2001, 2682–2683.

5210 Inorganic Chemistry, Vol. 49, No. 11, 2010
Abouelatta et al.
the achiral ligand Bn-TPEN. Compounds of the general
formula [Fe(II)(Bn-TPEN)X] all crystallize with the same
conformation (Figure 12, X = Cl), having the X group trans
to the basic amine donor N(1) and the three pyridyl donors
N(3)-N(5) adopting the mer geometry. In addition, two
pyridine N-donors, N(3) and N(4), adopt a coplanar con-
formation of their rings with respect to the Fe-X bond, while
the third donor ring containing N(5) is perpendicular to that
axis. Therefore, the fact that Bn-CDPy3 would prefer to
adopt the same conformation upon coordination to a metal
ion is not a surprise. On the basis of this analysis, three of the
conformers shown inFigure 9 (B, D, and E) can beeliminated
from consideration as the most stable because they do not
possess an X group trans to the basic amine donor N(1). Only
two complexes with Bn-CDPy3, conformers A and C, adopt
this preferred geometry. In the case of the Bn-TPEN complexes,
the energetic difference between A and C is not an issue, because
these conformers are enantiomers; therefore they are isoener-
getic. However, with the chiral ligand Bn-CDPy3, A and C
become diastereomeric; therefore they can exist at different
relative energies. It should be noted that the same conforma-
tional preference was assumed for the cation [FeIV(O)(Bn-
TPEN)]2þ based on paramagnetic 1H NMR data, which
indicated the same pattern of two downfield and one upfield
shift for the 2-pyridyl C-H resonances5 and on DFT calcula-
tions of conformational energies for different isomers.5,66
What is interesting in the case of Bn-CDPy3 is what
distinguishes conformations A from C. Both have the same
features: X group trans to N(1) and a mer geometry of three
pyridyl N-donors, with two coplanar and one perpendicular
to the M-X axis. Yet, conformation C is preferred over A by
greater than 2 kcal/mol in the Zn(II), Fe(II), and Co(III)
complexes. Our calculations have indicated that the origins of
energetic control over geometry are born from the ligand in
addition to the electronic preference (see ligand-metal inter-
actions, Table 4). Inspection of the calculated structures
indicates the ligand preference may be due to interactions
between the cyclohexane ring and the groups surrounding the
metal center. Namely, the calculations show 2.65 kcal/mol
stabilization for the ligand in conformation C relative to A
when the metal ion is removed from the Co(III) complex.
Upon inspection of the metal complexes, there are no
severe destabilizing interactions, such as eclipsing interac-
tions, that are readily apparent in A and not in C that would
explain why C is preferred. However, superimposing the
structures shown in Figure 13 gives some insight into the
origin of stereocontrol (additional figures can be found in
the Supporting Information). In order to visualize the over-
lap between the two structures in the most effective manner,
the enantiomer of structure A (ent-A) was generated to create
the same stereochemistry around the metal center, while the
stereochemistry of the diaminocyclohexane unit was in-
verted. The metal atom, the five nitrogens, and the chloride
were superimposed to produce the overlapped structures. As
shown in Figure 13, atoms surrounding the metal center
exhibit good overlap, with the exception of the top pyridyl
ring, which rotates slightly from structure C to ent-A. It is
clear in C that the methylene hydrogen atom can occupy the
cavity directly between two axial hydrogen atoms, as shown
in Figure 13. In ent-A, because the cyclohexane ring has
undergone a ring flip, an axial hydrogen atom occupies this
Figure 10. Comparison of calculated and observed chemical shifts of
the three protons in the 2-position on the pyridyl rings in isomer C of
[Co(Bn-CDPy3)Cl]2þ and [Zn(Bn-CDPy3)Cl]þ (R2 = 0.992).
˚
M-N bonds perpendicular to the πorbital (R(Zn-N5) 2.165 A
˚
and R(Zn-N1) 2.247 A, respectively).
Calculation of the excited states for isomer C of [Co(Bn-
CDPy3)Cl]2þ yields a weak transition at 532 nm comparable
to the weak absorption observed at 550 nm. The longest
wavelength transitions calculated for the other meridinal
isomers are in the same region (541 and 535 nm for A and
B, respectively); the transitions for the facial isomers were at
shorter wavelengths (490 and 505 nm for D and E, re-
spectively). Similar agreement is found for the iron complex:
isomer C of [Fe(Bn-CDPy3)Cl]2þ has a transition at 389 nm
compared to the observed transition at 413 nm.
The 1H NMR spectra for [Co(Bn-CDPy3)Cl]2þ and
[Zn(Bn-CDPy3)Cl]þ were calculated for comparison with
the experimental data. As shown in Figure 10, there is an
excellent correlation between the calculated and observed
chemical shifts for the three protons at the 2-position of the
pyridine rings. For each complex, two of the resonances are
downfield, while the third resonance is shifted upfield by
approximately 1.5 ppm. The upfield shift is due to the
shielding effect of the pyridyl ring situated directly below
the 2-pyridyl proton, as shown in Figure 11. A similar effect is
seen in calculations of the iron complex, but is complicated by
a very large paramagnetic contribution. Other isomers of the
cobalt, zinc, and iron complexes also show a large upfield
shift for 2-pyridyl protons that are directly above the π
system of a pyridyl ring (see Supporting Information).
Discussion
The experimental and theoretical data presented herein
indicate that the chiral pentadentate ligand Bn-CDPy3 dis-
plays a significant thermodynamic preference for adopting
the same coordination geometry in metal complexes of the
general formula [M(Bn-CDPy3)Cl], regardless of the metal
ion. This observation is noteworthy because five different
coordination geometries are possible for the chiral ligand
complexes of this formula. In the cases of the Co(III) and
Fe(II) complexes, X-ray crystallographic data were used to
determine the structure of the complexes. For the Zn(II)
complex, 1D and 2D NMR data were consistent with the
assigned structure. For the Fe(II), Co(III), and Zn(II) com-
plexes, the calculations agreed well with the experimental
data, including calculations that produced the same pattern
of two downfield and one upfield resonance in the 1H NMR
spectrum for the 2-pyridyl C-H groups of the Co(III) and
Zn(II) complexes.
In part, the origin of conformation control can be under-
stood by contrasting the data for Bn-CDPy3 complexes with
crystallographic data of the related complexes derived from
(66) Wang, Y.; Wang, Y.; Han, K. J. Biol. Inorg. Chem. 2009, 14, 533–545.

Article
Inorganic Chemistry, Vol. 49, No. 11, 2010 5211
Figure 11. Observed and calculated (in parentheses) chemical shifts for the 2-pyridyl C-H protons (shown in white, other protons omitted for clarity) of
(a) [Co(Bn-CDPy3)Cl]2þ and (b) [Zn(Bn-CDPy3)Cl]þ.
to move away fromthe C-H group. This rotation also affects
the bonding between the pyridine ring and the metal center,
˚
lengthening the distance by 0.018 A. These interactions may
explain both the ligand strain and ligand-metal binding
contributions to the difference inenergy betweenstructures A
and C in the Co(III) complexes. Similar interactions are
found in the Zn(II) and Fe(II) complexes.
Conclusion
In conclusion we have described the synthesis of the chiral
ligand (R,R)-Bn-CDPy3 and the characterization of zinc,
iron, and cobalt complexes derived from the ligand. Struc-
tural data for these complexes revealed that a single coordi-
nation geometry is favored, by at least several kcal/mol, in
metal complexes of Bn-CDPy3 out of five possible isomers.
Theoretical data, which were in good agreement with experi-
mental data, indicated that thepreferencefor creating a single
coordination geometry was due to both steric and electronic
Figure 12. Structure of the ligand Bn-TPEN and model of the cation
effects. Analysis of the calculated structures revealed some of
the key interactions that enforced a strong stereoisomeric
preference. Although the introduction of chirality into the
pentadentate ligand certainly introduced more complexity in
the coordination chemistry of the ligand relative to achiral
ligands of this class, this work proves that control over geometry
can be enforced and understood. A good understanding of these
factors will pave the way for a selective synthesis of enantiopure
complexes for applications in asymmetric catalysis.
[Fe(Bn-TPEN)Cl]þ generated using X-ray crystallographic data from
ref 10. The structure of the cation is similar to [Fe(Bn-CDPy3)Cl]þ, where
the Cl group is in a trans conformation relative to N(1) and the three
pyridyl N-donors N(3)-N(5) adopt a mer conformation, with two
pyridine N-donors residing in a coplanar conformation with respect to
the Fe-Cl bond, while the third ring is perpendicular to that axis.
Acknowledgment. J.J.K. would like to acknowledge Dr.
Bashar Ksebati for help with NMR studies, Dr. Mary
Jane Heeg for the X-ray crystallographic analysis, and
Wayne State University for its generous support of this
project. A.I.A. would like to thank the WSU IMR for
support. J.A.S. would like to thank Marco Allard and Dr.
Claudio Verani for their helpful discussions. H.B.S. and J.
A.S. gratefully acknowledge support from grants
CHE0910858 and GM058905-11, respectively.
Figure 13. Calculated structures of the dication [Co(Bn-CDPy3)Cl]2þ
C, ent-A(seeFigure 9), and an overlapofthe two structuresthatillustrates
the subtle differencesbetweenthetwostereoisomers. Allhydrogensexcept
those creating key interactions are omitted for clarity. In the case of C, a
methylene hydrogen can occupya position directly above the cyclohexane
ring and between two axial hydrogen atoms, whereas with ent-A, the
pyridyl substituent rotates to avoid an unfavorable interaction with a
closer axial hydrogen atom. See text for more details and Supporting
Information for additional figures.
Supporting Information Available: X-ray crystallographic
tables, cif files for compounds 5, 6, and 8, COSY, DEPT, HMQC,
and NOESY NMR spectra for compound 9, SCF energies
calculated with TPSS and B3LYP functionals, Cartesian coordi-
nates of compounds optimized with TPSS, full table comparing
calculated structures and crystal structures, and calculated proton
NMR chemical shifts for all structures. This material is available
free of charge via the Internet at http://pubs.acs.org.
space; so in order to avoid an unfavorable nonbonding
interaction, the 2-pyridyl methylene group rotates by 16°
and bends by 18° relative to the Co-N-N-N plane in order