Dalton

Transactions
View Article Online
PAPER View Journal | View Issue

Coordinatively- and electronically-unsaturated

Published on 02 November 2017. Downloaded by Universitat de Barcelona on 8/27/2020 5:18:33 PM.

Cite this: Dalton Trans., 2017, 46,

square planar cobalt(III) complexes of a pyridine
16228 dianionic pincer ligand†
Faidh Hana,a Alan J. Loughb and Gino G. Lavoie *a

Received 29th September 2017,
Accepted 2nd November 2017
DOI: 10.1039/c7dt03674d
rsc.li/dalton
A series of low-valent Co(III) square planar complexes supported by a dianionic pincer ligand bis(aryl-
amido)pyridine ([NNN]2−) was synthesized, including the first structurally characterized square planar
hydroxide complex ([NNN]Co(OH), 4) of a 3d transition metal in the +3 oxidation state. The magnetic pro-
perties of the Co(III) complexes were highly dependent on the charge of the complex and on the coordi-
nation environment of the metal. The diamagnetic cationic complex {[NNN]Co(py)}BF4 (2) can be con-
verted to neutral paramagnetic complexes [NNN]Co(OR) (R = Ph 3a, iPr 3b, and H 4) by a simple substi-
tution of the ancillary pyridine ligand in 2. The double bond character between the metal and the anilido
nitrogen was evident from short Co–N2,3 bond lengths in the solid-state structures, and further sup-
ported by density functional theory calculations. Complex 2 showed well-behaved redox processes at
−0.93 and +0.70 V assigned to CoII/III and [NNN]2−/1− redox couples, respectively. In contrast, both com-
plexes 3a and 4 showed some irreversibility in redox processes on either cobalt or ligands.

Introduction
Bis(amido)pyridine A (Fig. 1) is a class of pincer ligands based
on a pyridine backbone that is flanked by two anilide groups
through an alkyl linker, first utilized by McConville in 1995 as
a rigid dianionic tridentate ligand to support Ti,1 Zr,2 and Ta3
complexes. Interestingly, the coordination chemistry of bis
(amido)pyridine has been limited to early-transition metals
(Sc, Y and Re) and to lanthanides/actinides (La, Th, Nd, and
Fig. 1 Structures of the dianionic pincer ligands A and B.
a
Department of Chemistry, York University, 4700 Keele Street, Toronto, Ontario,
M3J 1P3, Canada. E-mail: glavoie@yorku.ca
b vation of bis(imino)pyridine Co(II)Cl2 with aluminoxanes,
X-Ray Laboratory, Department of Chemistry, University of Toronto, 80 St George
Street, Toronto, Ontario, M5S 1A1, Canada
† Electronic supplementary information (ESI) available: Crystallographic data for
2, 3a and 4 in CIF and other electronic format, including tables of crystal data
and structure refinement, bond lengths, angles, atomic coordinates and equi-
valent isotropic displacement parameters, and anisotropic displacement para-
meters. NMR spectra for 2, 3a, 3b and 4. DFT optimized coordinates and mole-
cular orbital diagrams for 2, 3a and 4. CCDC 1571906–1571908. For ESI and crys-
tallographic data in CIF or other electronic format see DOI: 10.1039/c7dt03674d
Lu),4–11 with only one report on Fe, Co, and Ni complexes.12
An analogous ligand with an isopropylene linkage between the
central pyridine ring and the anilide groups was reported and
discovered serendipitously by Wang13 while studying the tri-
methylaluminum complexes of bis(imino)pyridine, which
undergoes methyl insertions to give B (Fig. 1). This family of
ligands A and B is highly rigid, coordinating to the metal
centers in a meridional fashion, and allows for easy variations
of its steric and electronic properties. These bis(amido)pyri-
dine ligands are formally 6-electron σ-donors, with additional
π-electron density donation available from the anilide nitrogen
atoms. This electron-donating ability of the ligand offers the
opportunity to stabilize electron-poor metal centers in coordi-
natively-unsaturated complexes.
We became interested in studying the coordination chem-
istry of these ligands to cobalt(III) complexes for potential use
in olefin polymerization. [NNN]CoR presents interesting simi-
larities to the bis(imino)pyridine cobalt(II) systems, which are
highly active in olefin polymerization. [NNN]CoR closely
resembles the catalytically-active species obtained by the acti-
without being positively charged, thus decreasing the propen-
sity of functional groups present in monomers such as acry-
lates from impeding and even poisoning catalysis.14,15 Gibson
further suggested that the propagating species could in fact
involve a Co(III) dialkyl zwitterionic complex.16 Organocobalt(III)
systems have also been shown to be active in olefin polymeriz-
ation, even in the absence of a cocatalyst.17 [NNN]CoR com-

16228 | Dalton Trans., 2017, 46, 16228–16235 This journal is © The Royal Society of Chemistry 2017

Dalton Transactions
plexes are also excellent candidates in controlled radical
polymerization,18 and in olefin hydrogenation, a transform-
ation that continues to be of great interest thanks to recent
developments in the use of earth-abundant metal-based
catalysts.19
We thus herein report the synthesis of cobalt(III) cationic
and neutral square planar complexes of the tridentate [NNN]2−
ligand, including the first isolated and structurally-character-
Published on 02 November 2017. Downloaded by Universitat de Barcelona on 8/27/2020 5:18:33 PM.
ized 3d metal hydroxide complex. To minimize the possible
undesired participation of the ligand in β-hydride elimination,
our initial study focused on the use of ligand class B. Features
from the solid-state structures of the isolated complexes are
presented, along with their electrochemical behavior and
results from density functional theory calculations.
Results and discussion
Preparation and reactivity of cobalt(III) complexes
The synthesis of complex 1 was adopted from that reported by
Summerscales and Gordon,12 where an alkyl lithium base was
added to a cold suspension of H2[NNN] and Co(II)Cl2py4. The
1
H NMR spectrum of the paramagnetic complex 1 showed four
(20.6, 17.1, 1.1 and −4.4 ppm) very broad resonances. Complex
1 was readily oxidized by AgBF4 to give the blue diamagnetic
coordinatively-unsaturated square planar Co(III) complex 2
(Scheme 1).30 The resonances in the 1H and 13C NMR spectra
of 2 were unambiguously assigned by 2D correlation experi-
ments. The fluoride nucleus in the tetrafluoroboride countera-
nion resonates at −152.5 ppm in the 19F NMR spectrum.
Complex 2 is insoluble in water but soluble and stable in
protic (methanol) and polar organic (dichloromethane) sol-
vents. The complex is relatively stable in air, with minimal
decomposition observed after prolonged exposure of up to 4
weeks.
The synthesis of the corresponding neutral alkyl and
hydride complexes was explored by reactions of 2 with metal
alkyl and hydride reagents, such as AlMe3, CH2CHCH2MgCl,
CH3MgBr, LiCH2Si(CH3)3, and LiHB(CH2CH3)3. These reac-
tions gave a reduced product, presumably through homolytic
cleavage of the metal–hydrogen or metal–carbon bond in the
new transiently-formed complex, resulting in a red para-
magnetic complex, consistent with 1 based on spectroscopic
data.31–34 This was further supported by the independent syn-
thesis of complex 1 by the chemical reduction of 2 with KC8.
Reactions of 2 with sodium phenoxide and isopropoxide to
produce coordination complexes [NNN]Co(III)OR (R = Ph 3a
and iPr 3b) were explored (Scheme 2). Complexes 3a and 3b
displayed a paramagnetically-shifted 1H NMR spectrum with
Scheme 1 Synthesis of complex 1 and 2.
This journal is © The Royal Society of Chemistry 2017
View Article Online
Paper
Scheme 2 Synthesis of complexes 3 and 4.
relatively sharp resonances (average ν1/2 (Hz) for all methyl
resonances: 6.7 (3a) and 31 (3b)), and chemical shifts ranging
from 26 to −10 ppm for 3a, and from 47 to −11 ppm for 3b.
Single crystals of 3a suitable for X-ray diffraction analysis were
obtained by liquid diffusion of pentane into a dichloro-
methane solution of 3a at low temperatures. The crystals of
complex 3b could not be isolated due to reactivity towards
adventitious water. While analysis of the reaction mixture by
1
H NMR spectroscopy (see the ESI†) supported the formation
of 3b, attempts to isolate the product through standard wash-
ings and extractions led to the formation of the paramagnetic
hydroxo complex 4, which was independently prepared by the
reaction of 2 with either sodium or cesium hydroxide.
Complex 4 could also be generated by protonolysis of 3a
with water. The UV-visible spectrum of 4 resembled that of the
Co(III) complexes 2 and 3a. The resonances observed in the
relatively sharp (average ν1/2 for all methyl resonances: 13 Hz)
paramagnetically-shifted (δ 48 to −11 ppm) 1H NMR spectrum
of 4 are consistent with the expected structure. The hydroxy
resonance was however not observed. The X-ray diffraction ana-
lysis of complex 4 corroborated the structure and the coordi-
nation of the hydroxy ligand to the metal. The hydrogen atom
was successfully located on the differential electron density
map, eliminating the need to use the calculated position in a
riding model to confirm the molecular structure (vide infra).
A search of the Cambridge Crystallographic Data Center
(CCDC) database revealed that complex 4 represents the first
structurally characterized cobalt(III) hydroxide complex and
the first square planar first-row transition metal in the +3
oxidation state with a terminal hydroxide.
The spin-only magnetic moment for 3a and 4, respectively,
was determined in THF-d8 at room temperature by the Evans
method and found to be of 2.4 and 2.7µB, consistent with two
unpaired electrons. Complex 3b could not be isolated in a pure
enough form to allow for magnetic susceptibility measure-
ments. The paramagnetism of 3 based on Co(II) oxyl radical
species is ruled out based on crystallographic35–37 and
spectroscopic38–40 data. Complexes 3a and 4 (and most likely
3b) thus adopt a low-lying triplet ground state (S = 1, as pre-
dicted by DFT calculations, vide infra) at room temperature,
commonly observed in square planar Co(III) complexes.41–43
Dalton Trans., 2017, 46, 16228–16235 | 16229
 View Article Online

Paper Dalton Transactions

X-ray studies
X-ray diffraction analysis on single crystals was used to deter-
mine the solid-state structure for complexes 2, 3a and 4. All
complexes adopt a slightly-distorted square planar geometry in
the solid state, with four-coordinate geometry index (τ4) values
of 0.09, 0.10, and 0.11, respectively (Fig. 2).44 The cobalt is
positioned within 0.03 (2, 4) to 0.09 Å (3a) from the mean
plane formed by the three nitrogen atoms of the [NNN]2−
Published on 02 November 2017. Downloaded by Universitat de Barcelona on 8/27/2020 5:18:33 PM.

ligand. The sum of the angles of the amido nitrogen atoms

ranges from 359.0 to 360.0°, highlighting the trigonal planar geo-
metry and the sp2 hybridization of N2,3, which allows for the
enhanced stability of these otherwise electronically-unsaturated
metal centers through the donation of π-electron density to
empty d-orbitals on the metal (vide infra). The cobalt amide bond
lengths (Co–N) in 2 are unusually short, with an average of
1.792 Å. These bond lengths are in fact the shortest cobalt(III)–
amide bonds reported in the CCDC database. Co–NR2 single
bond lengths normally range from 1.87 to 1.92 Å,45–50 while
CovNR double bond lengths range from 1.66 to 1.69 Å.51–53
The coordinating amido groups enforce a much shorter
Co–N1[NNN] pyridine bond length in 2 (1.829(3) Å), compared to
Co–N4pyridine (1.938(3) Å) (Table 1). The corresponding Co–N1
bond in 3a remains unchanged at 1.829(2) Å but elongates to
1.8573(16) Å in 4. Likewise, the Co–NR2 bonds in 2 and 3a are
statistically equivalent, but they are elongated in 4. The Co–O1
and O1–C28 bond lengths in 3a are 1.8984(17) Å and 1.329(3)
Å, respectively, well within the literature values of Co-bonded
anionic phenoxide ligands.37,39,40,54,55 The phenoxide is
almost perpendicular (85°) to the mean plane formed by N1,
N2 and N3, with a C28–O1–Co–N2 torsional angle of 81°. The
Co–O1 bond length (1.7945(15) Å) in complex 4 is shorter than
that reported in other 3d transition metal complexes contain-
ing a terminal hydroxide ligand.56 The planes formed by xylyl
groups in 2, 3a, and 4 are 80–86° to the plane formed by the
[NNN]2− ligand.

Cyclic voltammetry
Cyclic voltammetry of the cationic complex 2 in dichloro-
methane shows a reversible one-electron CoII/III couple at
−0.93 V, and a ligand-based ([NNN]2−/[NNN]1−) quasi-revers-
ible one-electron couple at 0.70 V (Fig. 3). The metal-based
redox couple in the neutral complex 3a occurs at a higher
negative potential (−1.47 V), with two oxidation peaks (Epa) at
−0.02 V and 0.89 V, centered on the organic fragments.
Complex 4 shows an irreversible reduction of Co(III) at −1.82 V
and a [NNN]2− ligand-based reversible one-electron redox Fig. 2 ORTEP representations of 2 (top), 3a (middle), and 4 (bottom)
process at 0.00 V. DFT calculations (vide infra) predict that the (50% probability level). Most hydrogen atoms, the BF4 counteranion in 2
redox events at Epa 0.80 (2) and 0.05 V (4) occur on the [NNN]2− and solvent molecules in 3a and 4 were removed for clarity. Selected
ligand itself, while the irreversible anodic peaks for 3a involve bond lengths and angles are presented in Table 1.

both the phenoxide (Epa −0.02 V) and [NNN]2− (Epa 0.89 V)

ligands. Thus, the potentials for the oxidation of the [NNN]2−
ligand in 2 ([NNN]Co( py)1+) and [3a]+ ([NNN]Co(OPh)1+) are
within 0.09 V of each other and, as expected based on the
greater charge of the complexes, approximately 0.80 V higher
than that for 4 ([NNN]Co(OH)).
Density functional theory calculations
Density functional theory (DFT) calculations were performed
on complexes 2, 3a and 4. The geometry of these complexes
was optimized at the B3LYP level of theory using the LANL2DZ

16230 | Dalton Trans., 2017, 46, 16228–16235 This journal is © The Royal Society of Chemistry 2017
 View Article Online

Dalton Transactions Paper

Table 1 Selected bond lengths (Å) and bond angles (°) for complexes 2,
3a and 4

Complexes 2 3a 4

Co–N1 1.829(3) 1.829(2) 1.8573(16)

Co–N2 1.788(3) 1.790(2) 1.8363(16)
Co–N3 1.796(2) 1.796(2) 1.8392(16)
Co–N4 1.938(3)
Co–O1 1.8984(17) 1.7945(15)
Published on 02 November 2017. Downloaded by Universitat de Barcelona on 8/27/2020 5:18:33 PM.

N1–Co–N2 84.86(13) 84.93(10) 84.16(7)

N1–Co–N3 84.58(12) 84.73(10) 83.64(7)
N2–Co–N3 169.42(13) 168.52(10) 167.71(7)
N1–Co–N4 178.33(13)
N1–Co–O1 177.03(9) 177.17(7)
Co–O1–C28 120.86(16)
Fig. 3 Cyclic voltammograms of 2 (dotted), 3a (dashed), and 4 (solid
line) in dichloromethane containing 0.1 M Bu4N(PF6), using ferrocene as
the internal standard (E1/2 = 0.00 V; scan rate 100 mV s−1).
basis set, and calculations were performed in the singlet state
and in the unrestricted triplet state. Energies were calculated
on the optimized structure with the triple-zeta valence polar-
ized basis set (def-TZVP). Similar methods have been used to
study Co systems.37,57 These calculations indicate that the
triplet state is more energetically favored than the singlet state
by approximately 7 kcal mol−1 (3a) and 16 kcal mol−1 (3b, 4).
In contrast, both spin states for the cationic complex 2 have
approximately the same energy (within 0.1 kcal mol−1). These
calculations thus support the observed diamagnetism of
complex 2 and paramagnetism of complexes 3 and 4.
The composition of the frontier orbitals in the molecular
orbital diagram of complexes 2, 3a and 4 was analyzed using
the AOMix software28,29 where the complexes were split into
three fragments: Co3+, [NNN]2−, and the second donor ( py in
2, −OPh in 3a, or −OH in 4). AOMix28,29 was also used to match
the α- and β-orbitals of the paramagnetic complexes and quan-
tify the quality of the match with the resemblance factor q on a
scale from 0 ( poor) to 1 (excellent; see the ESI†).
The lowest unoccupied molecular orbital (LUMO) of
complex 2 consists of a π*-antibonding interaction between
the dxz orbital on cobalt and pz orbitals on the amide nitrogen
atoms. The corresponding π(dxz,pz)-bonding interaction corres-
ponds to the HOMO−10, indicating a Co–N bond order of 1.5,
consistent with the short Co–N2,3 bond length observed in the
Fig. 4 π-(HOMO−10) and π*-(LUMO) molecular orbitals for the Co–
N2,3 bonds in complex 2 (isovalue of 0.04 e− Å−3).
solid-state structure of 2 (Fig. 4). The [NNN]2− contributes at
least 85% of the electron density for the highest occupied
molecular orbitals HOMO to HOMO−4, with the electron
density in the HOMO to the HOMO−2 solely localized on the
xylyl groups, predicting possible oxidation of the ligand as
observed in the cyclic voltammetry.
The composition of the two lowest singly unoccupied mole-
cular orbitals (LSUMO and LSUMO+1) in complex 3a is split
approximately equally between the cobalt atom (55%) and the
[NNN]2− ligand (45%). The LSUMO+1 is a π*-orbital arising
from dxz,pz-interactions between cobalt (dxz) and nitrogen ( pz),
with the corresponding (also antibonding) singly occupied
molecular orbital HSOMO−3 (q = 0.81). The short Co–N bond
lengths observed in the solid-state structure of 3a are further
supported by other π-bonding interactions (HSOMO−15 and
HSOMO−53; see the ESI†). The two highest singly occupied
molecular orbitals (HSOMO and HSOMO−1), with an energy
difference of only 1.3 kcal mol−1, are related to each other (q =
1.0) and principally localized (96%) on the phenoxide ligand
(Fig. 5). The next four lower energy α-orbitals matched with
their β-orbitals with q > 0.90. Orbital sets HSOMO−5/
HSOMO−4 and HSOMO−9/HSOMO−8 are mainly composed
of the [NNN]2− fragment (>94%), while HSOMO−6/HSOMO−7
and HSOMO−11/HSOMO−10 are composed of both [NNN]2−
and −OPh fragments in ratios of approximately 30 : 70 and
75 : 25, respectively. These data support the ability of both
[NNN]2− and −OPh to easily get oxidized, as observed in the
cyclic voltammetry.
Fig. 5 HSOMO and HSOMO−1 of complex 3a (0.045 e− Å−3).

This journal is © The Royal Society of Chemistry 2017 Dalton Trans., 2017, 46, 16228–16235 | 16231

Paper
As for complex 4, the lowest unoccupied orbitals LSUMO+1
and LSUMO (q = 0.67) are composed of 98% and 58%, respect-
ively, of the pyridine π-system from the [NNN]2− ligand. As
observed in 3a, the HSOMO and LSUMO+2 (q = 0.81) of
complex 4 are also π-antibonding, arising from interactions
between dxz,pz-atomic orbitals. As noted for 2 and 3a,
additional π-bonding molecular orbitals (HSOMO−11 and
HSOMO−38) result in short Co–N bond lengths (see the ESI†).
Published on 02 November 2017. Downloaded by Universitat de Barcelona on 8/27/2020 5:18:33 PM.
Orbital sets HSOMO−3/HSOMO−2, HSOMO−4/HSOMO−5,
HSOMO−8/HSOMO−7, and HSOMO−10/HSOMO−9 are com-
posed of more than 95% of the [NNN]2− fragment with most of
the electron density again localized on the xylyl rings. In con-
trast, the electron density in the orbital set HSOMO−6/
HSOMO−1 exhibits significant amido N pz-character. The DFT
calculations thus proved helpful in interpreting the observed
electrochemistry for complexes 2, 3a and 4.
All complexes show a large Co contribution (>50% for 2 and
3a, 35% for 4) to the lowest unoccupied molecular orbitals
indicating that cathodic peaks at −0.93 (2), −1.47 (3a) and
−1.82 V (4) correspond to the reduction of Co(III) to Co(II). In
contrast, the highest occupied molecular orbitals are generally
localized on either the [NNN]−2 or −OPh/−OH ligands with
small (less than 15%) Co contribution. Orbitals with >15% Co
contribution are at least 18 kcal mol−1 lower in energy than
the highest occupied molecular orbitals (HOMO in 2 or
HSOMO in 3a and 4), indicating that the redox couples at 0.70
(2) and 0.00 V (4) and anodic peaks at −0.02 and 0.89 V (3a)
are all principally ligand-based. Specifically, these ligand-
based activities are localized on the xylyl ring for complex 2,
and on either the xylyl ring or the amido groups for complex 4.
The HSOMO and HSOMO−1 orbitals of complex 3a are loca-
lized on the aromatic phenoxide ring, with the xylyl groups
heavily contributing to the HSOMO−2 to the HSOMO−5. This
suggests that the anodic peaks at −0.02 and 0.89 V correspond
to the oxidation of the phenoxide phenyl ring and of the xylyl
group of the [NNN]2− ligand, respectively.
Conclusions
A series of low valent Co(III) square planar complexes sup-
ported by a dianionic pincer bis(arylamido)pyridine ligand was
synthesized and characterized, including an unprecedented
and first ever structurally-characterized square planar Co(III)
hydroxide complex. The magnetic properties of these com-
plexes were found to be highly dependent on the charge and
nature of the coordination sphere imparted by the second
ligand, chosen from either pyridine, phenoxide or hydroxide.
While the cationic pyridine complex 2 is diamagnetic, com-
plexes 3 and 4 exhibit paramagnetism with two unpaired elec-
trons. The double bond character between the metal and the
anilido nitrogen was evident from X-ray diffraction analysis
and further supported by DFT calculations for complex 2.
Complex 2 showed well-behaved redox chemistry. In contrast,
both complexes 3a and 4 showed irreversible redox processes
on either cobalt or ligands. The corresponding hydride and
16232 | Dalton Trans., 2017, 46, 16228–16235
View Article Online
Dalton Transactions
alkyl complexes could not be isolated, presumably due to their
high reactivity and homolysis of the new bond formed. Our
present work is focused on utilizing these complexes in
polymerization of alkenes and lactides, and in hydrogenation
of alkenes. The results will be reported in due course.
Experimental
General considerations
Unless otherwise noted, all manipulations were carried out
using oven-dried glassware and performed under argon using
standard Schlenk line techniques or in a nitrogen-filled
mBraun glovebox. Solvents were dried using an mBraun
solvent purification system (MB-SPS) fitted with alumina
columns and stored over molecular sieves under argon.
Deuterated NMR solvents were purchased from Sigma-Aldrich,
degassed using three freeze–pump–thaw cycles, vacuum dis-
tilled from Na/benzophenone (C6D6) and CaH2 (CD2Cl2), and
stored under argon or nitrogen. NMR spectra were recorded on
a Bruker DRX 600, Bruker AV 400 or Bruker AV 300 spectro-
meter at room temperature. CoCl2py4 20 was synthesized
according to the literature procedures. Sodium isopropoxide
and sodium phenoxide were prepared from the corresponding
alcohol and sodium metal. Bu4NPF6, CoCl2 and AgBF4, and
LiCH2SiMe3 (1.0 M in pentane) were purchased from Sigma-
Aldrich and used as received.
Synthetic procedures
[NNN]Co( py) (1). Complex 1 was prepared following an
experimental procedure reported by Summerscales and
Gordon for a related complex.12 To a 50 mL toluene suspen-
sion of H2[NNN] (2.23 g, 5.00 mmol) and CoCl2py4 (2.01 g,
5.00 mmol) cooled to −40 °C was added LiCH2SiMe3 (1.0 M in
pentane; 10.5 mL, 10.5 mmol), resulting in a color change
from cyan to red. After stirring overnight at room temperature,
the mixture was filtered using a cannula filter, and the volatiles
were evaporated under vacuum. The crude red solids were
washed with cold pentane and dried under vacuum. Yield:
1.84 g, 3.45 mmol, 69%.
{[NNN]Co( py)}BF4 (2). A 20 mL toluene solution of complex
1 (1.84 g, 3.43 mmol) was added to a 20 mL toluene suspen-
sion of AgBF4 (0.667 g, 3.43 mmol) at room temperature and
the mixture was stirred for 2 h. The supernatant was removed,
and the residual solids were washed with toluene. The product
was extracted with dichloromethane, and the volatiles from
the solution removed in vacuo to yield a dark blue solid
(1.90 g, 3.09 mmol, 90%). Crystals for X-ray crystallography
were grown by liquid diffusion of pentane into a dichloro-
methane solution of 2. 1H NMR (400 MHz; CD2Cl2): δ 9.60 (d,
3
J = 5.2 Hz, 2H, o-CHpy), 8.54 (t, 3J = 8.0 Hz, 1H, p-CH) 7.79 (d,
3
J = 7.9 Hz, 2H, m-CH), 7.72 (t, 3J = 7.5 Hz, 1H, p-CHpy), 7.15
(dd, 2H, m-CHpy), 6.77 (t, 3J = 7.6 Hz, 2H, p-CHxylyl ), 6.45 (d,
3
J = 7.4 Hz, 4H, m-CHxylyl ), 1.90 (s, 12H, CH3(xylyl)), 1.29 (s, 12H,
C(CH3)2). 13C{1H} NMR (100 MHz, CD2Cl2): δ 172.4 (o-C), 155.4
(o-Cpy), 152.2 (o-Cxylyl ), 140.8 ( p-C), 139.1 ( p-Cpy), 128.3 (m-
This journal is © The Royal Society of Chemistry 2017

Dalton Transactions
Cxylyl ), 127.1 (ipso-Cxylyl ), 125.5 ( p-Cxylyl, and m-Cpy), 119.7
(m-C), 91.8 (C(CH3)2), 23.0 (C(CH3)2), 21.5 (CH3xylyl ). 19F NMR
(376 MHz; CD2Cl2): δ −152.5 (s, BF4). Anal. calcd for
C32H38N4CoBF4: C, 61.55; H, 6.13; N, 8.97. Found: C, 61.29; H,
5.87; N, 8.58.
[NNN]Co(OPh) (3a). A 5 mL dichloromethane solution of 2
(106 mg, 0.170 mmol) was added to a 5 mL dichloromethane
suspension of sodium phenoxide (22.6 mg, 0.185 mmol)
Published on 02 November 2017. Downloaded by Universitat de Barcelona on 8/27/2020 5:18:33 PM.
resulting in a slight colour change to a lighter blue. The
mixture was stirred at room temperature for 1 h, filtered and
dried in vacuo. The product was isolated by extraction with
toluene. The volatiles were removed in vacuo and the blue solid
was further washed with pentane (5 × 25 mL). Yield 64 mg,
0.12 mmol, 68%. Crystals for X-ray crystallography were grown
from pentane liquid diffusion into dichloromethane solution
stored at −40 °C. 1H NMR (400 MHz; C6D6): δ 26.49 (d, 3J =
7.1 Hz, 4H, m-CHxylyl ), 13.31 (dd, 2H, m-CHPh), 10.73 (t, 3J =
7.1 Hz, 2H, p-CHxylyl ), 3.59 (t, 3J = 6.8 Hz, 1H, p-CHPh), 2.94 (d,
3
J = 7.2 Hz, 2H, m-CH), 2.60 (t, 3J = 7.0 Hz, 1 H, p-CH), 2.21 (s,
12H), −3.91 (s, 12H), −9.74 (d, 3J = 7.0 Hz, 2H, o-CHPh).
13
C{1H} NMR (100 MHz; C6D6): δ 246.2, 200.5, 172.5, 137.1
126.8, 108.8, −22.1. Magnetic moment (THF, 0.05 M): 2.4 B.M.
Anal. calcd for C33H38CoN3O: C, 71.85; H, 6.94; N, 7.62. Found:
C, 71.59; H, 7.17; N, 7.38.
[NNN]Co(OiPr) (3b). Complex 3b was prepared using the pro-
cedures described for 3a on a 0.167 mmol scale. The formation
of 3b is consistent with 1H NMR spectroscopic data but could
not be cleanly isolated due to rapid decomposition. 1H NMR
(400 MHz; C6D6): δ 47.29 (br, 4H, m-CHxylyl ), 35.06 (br, 1H,
OCH(CH3)2), 15.72 (br, 2H, p-CHxylyl ), 6.44 (br, 6H, OCH
(CH3)2), 0.42 (br, 2H, m-CH), 0.04 (12H), −3.90 (br, 1H, p-CH),
−10.90 (12H).
[NNN]Co(OH) (4). To a 5 mL dichloromethane solution of
complex 2 (79 mg, 0.13 mmol) was added excess NaOH pellets
(or CsOH·H2O), with no attempt to exclude moisture or air
from the reaction mixture. The reaction mixture was stirred
vigorously for 1 h at room temperature. The mixture was
filtered, and the solvent from the filtrate evaporated. The
product was extracted using toluene. The solvent was evapor-
ated and the product was washed with warm hexanes to give 4
as a purple solid (47 mg, 0.10 mmol, 77%). Crystals for X-ray
crystallography were grown from a dichloromethane/pentane
mixture stored at 0 °C. 1H NMR (400 MHz; C6D6): δ 48.58 (d,
3
J = 7.3 Hz, 4H, m-CHxylyl ), 14.90 (t, 3J = 7.2 Hz, 2H, p-CHxylyl ),
2.71 (s, 12H), 0.21 (d, 3J = 7.0, 2H, m-CH), −9.98 (s, 12H),
−11.04 (t, 3J = 6.9 Hz, 1H, p-CH). 13C NMR (150 MHz; C6D6):
δ 322.8, 297.2, 244.1, 128.9, 91.5, −63.5, −110.0. Magnetic
moment (THF, 0.05 M): 2.7 B.M. Anal. calcd for C27H34CoN3O:
C, 68.05; H, 7.40; N, 8.82. Found: C, 68.31; H, 7.28; N, 8.55.
Cyclic voltammetry
Cyclic voltammograms were produced using a BASi-Epsilon
potentiostat on dichloromethane solutions of the analytes
(0.01 M) containing 0.1 M Bu4NPF6 as the electrolyte. A plati-
num disc (1 mm diameter) and a platinum wire were used as
working and auxiliary electrodes, respectively. A silver wire
This journal is © The Royal Society of Chemistry 2017
View Article Online
Paper
coated with AgCl was used as the reference electrode. All
potentials were calibrated vs. the Fc+/Fc redox couple. Half-
wave potential (E1/2) was estimated as the average of anodic
(Epa) and cathodic peak (Epc) potentials.
Computational details
Geometry optimizations were carried out at the B3LYP21–24
hybrid level of theory with the LANL2DZ basis set using
Gaussian 09,25 with GaussView 0326 for molecular visualiza-
tion. These calculations were performed on the Shared
Hierarchical Academic Research Computing Network
(SHARCNET: http://www.sharcnet.ca). The starting geometries
were based on X-ray structures but further optimized in the
gas phase. Energy calculations were performed at the same
functional using the triple-zeta valence polarized basis set
(def-TZVP).27 The composition of molecular orbitals as combi-
nations of atomic orbitals was determined based on data
generated by Gaussian 09 using AOMix software.28,29
X-ray crystallography
Crystallographic data were collected at the University of
Toronto on a Bruker Kappa APEX-DUO diffractometer using
monochromated Mo-Kα radiation (Bruker Triumph; λ =
0.71073 Å) at 150 K. Data were measured using a combination
of ϕ scans and ω scans, and were processed using APEX2 and
SAINT.58 Absorption corrections were carried out using
SADABS.58 Structures were solved with WinGX59 or OLEX260 as
the graphical user interface using either SHELXL or SHELXT
with SHELXS-97 for full-matrix least-squares refinement that
was based on F2.61–63 All H atoms were included in calculated
positions, except for the hydroxy hydrogen atom in 4, and
allowed to refine in riding-motion approximation with Uiso
tied to the carrier atom.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
G. G. L. gratefully acknowledges financial support from the
Natural Sciences and Engineering Research Council for a
Discovery Grant. F. H. wishes to thank Enbridge and the
Government of Ontario for scholarships. The authors wish to
thank Professor A. B. P. Lever and Dr Elaine Dodsworth for
helpful discussion of DFT calculations.
References
1 F. Guérin, D. H. McConville and J. J. Vittal, Organometallics,
1997, 16, 1491–1496.
2 F. Guérin, D. H. McConville and J. J. Vittal, Organometallics,
1996, 7333, 5586–5590.
Dalton Trans., 2017, 46, 16228–16235 | 16233

Paper
3 F. Guérin, D. H. McConville and J. J. Vittal, Organometallics,
1995, 14, 3154–3156.
4 F. Estler, G. Eickerling, E. Herdtweck and R. Anwander,
Organometallics, 2003, 22, 1212–1222.
5 C. A. Cruz, D. J. H. Emslie, L. E. Harrington, J. F. Britten
and C. M. Robertson, Organometallics, 2007, 26,
692–701.
6 C. A. Cruz, D. J. H. Emslie, H. A. Jenkins and J. F. Britten,
Published on 02 November 2017. Downloaded by Universitat de Barcelona on 8/27/2020 5:18:33 PM.
Dalton Trans., 2010, 39, 6626–6628.
7 S. Jie and P. L. Diaconescu, Organometallics, 2010, 29,
1222–1230.
8 C. P. Lilly, P. D. Boyle and E. A. Ison, Dalton Trans., 2011,
40, 11815–11821.
9 C. P. Lilly, P. D. Boyle and E. A. Ison, Organometallics, 2012,
31, 4295–4301.
10 H. Sugiyama, S. Gambarotta, G. P. A. Yap, D. R. Wilson and
S. K.-H. Thiele, Organometallics, 2004, 23, 5054–5061.
11 M. Zimmermann, F. Estler, E. Herdtweck, K. W. Törnroos
and R. Anwander, Organometallics, 2007, 26, 6029–6041.
12 O. T. Summerscales, J. A. Stull, B. L. Scott and J. C. Gordon,
Inorg. Chem., 2015, 54, 6885–6890.
13 B. Y. Tay, C. Wang, S. C. Chia, L. P. Stubbs, P. K. Wong and
M. Van Meurs, Organometallics, 2011, 30, 6028–6033.
14 V. C. Gibson, M. J. Humphries, K. P. Tellmann, D. F. Wass,
A. J. P. White and D. J. Williams, Chem. Commun., 2001,
120, 2252–2253.
15 T. M. Kooistra, Q. Knijnenburg, J. M. M. Smits,
A. D. Horton, P. H. M. Budzelaar and A. W. Gal, Angew.
Chem., Int. Ed., 2001, 113, 4719–4722.
16 M. J. Humphries, K. P. Tellmann, V. C. Gibson,
A. J. P. White and D. J. Williams, Organometallics, 2005, 24,
2039–2050.
17 O. Daugulis, M. Brookhart and P. S. White,
Organometallics, 2003, 22, 4699–4704.
18 A. Debuigne, R. Poli, C. Jérôme, R. Jérôme and
C. Detrembleur, Prog. Polym. Sci., 2009, 34, 211–239.
19 S. A. M. Smith, P. O. Lagaditis, A. Lüpke, A. J. Lough and
R. H. Morris, Chem. – Eur. J., 2017, 23, 7212–7216.
20 D. Zhu, F. F. B. J. Janssen and P. H. M. Budzelaar,
Organometallics, 2010, 29, 1897–1908.
21 P. J. Stephens, F. J. Devlin, C. F. Chabalowski and
M. J. Frisch, J. Phys. Chem., 1994, 98, 11623–11627.
22 S. H. Vosko, L. Wilk and M. Nusair, Can. J. Phys., 1980, 58,
1200–1211.
23 C. Lee, W. Yang and R. G. Parr, Phys. Rev. B: Condens.
Matter, 1988, 37, 785–789.
24 A. D. Becke, J. Chem. Phys., 1993, 98, 5648–5652.
25 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, V. Scalmani, G. Barone,
B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng,
J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda,
J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, T. Vreven, J. A. Montgomery Jr., J. E. Peralta,
F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers,
K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand,
16234 | Dalton Trans., 2017, 46, 16228–16235
View Article Online
Dalton Transactions
K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar,
J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene,
J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo,
R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin,
R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin,
K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador,
J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas,
J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox,
Gaussian 09, Revision D.01, Wallingford CT, 2013.
26 R. D. Ik, T. Keith, J. Millam, K. Eppinnett, I. W. Hovell and
R. Gilliland, GaussView 3, Carnegie PA, 2003.
27 F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys., 2005,
7, 3297.
28 S. I. Gorelsky and A. B. P. Lever, J. Organomet. Chem., 2001,
635, 187–196.
29 S. I. Gorelsky, AOMix: Program for Molecular Orbital
Analysis, Version 6.88, University of Ottawa, Ottawa,
Canada, 2013.
30 J. Y. Jeon, J. J. Lee, J. K. Varghese, S. J. Na, S. Sujith,
M. J. Go, J. Lee, M. Ok and B. Y. Lee, Dalton Trans., 2013,
42, 9245–9254.
31 S. Maria, H. Kaneyoshi, K. Matyjaszewski and R. Poli,
Chem. – Eur. J., 2007, 13, 2480–2492.
32 M. D. Fryzuk, D. B. Leznoff, R. C. Thompson and
S. J. Rettig, J. Am. Chem. Soc., 1998, 120, 10126–10135.
33 J. Setsune, Y. Ishimaru, T. Moriyama and T. Kitao, J. Chem.
Soc., Chem. Commun., 1991, 555.
34 M. S. Ram, C. G. Riordan, G. P. A. Yap, L. Liable-Sands,
A. L. Rheingold, A. Marchaj and J. R. Norton, J. Am. Chem.
Soc., 1997, 119, 1648–1655.
35 A. Sokolowski, E. Bothe, E. Bill, T. Weyhermüller,
K. Wieghardt, H. Stratemeier, D. Reinen and P. F. Knowles,
Chem. Commun., 1996, 28, 1671–1672.
36 B. Adam, E. Bill, E. Bothe, B. Goerdt, G. Haselhorst,
K. Hildenbrand, A. Sokolowski, S. Steenken,
T. Weyhermüller and K. Wieghardt, Chem. – Eur. J., 1997, 3,
308–319.
37 A. S. Roy, N. Muresan, H. M. Tuononen, S. P. Rath and
P. Ghosh, Dalton Trans., 2008, 3438.
38 A. Kochem, H. Kanso, B. Baptiste, H. Arora, C. Philouze,
O. Jarjayes, H. Vezin, D. Luneau, M. Orio and F. Thomas,
Inorg. Chem., 2012, 51, 10557–10571.
39 A. Sokolowski, B. Adam, T. Weyhermüller, A. Kikuchi,
K. Hildenbrand, R. Schnepf, P. Hildebrandt, E. Bill and
K. Wieghardt, Inorg. Chem., 1997, 36, 3702–3710.
40 L. Benisvy, E. Bill, A. J. Blake, D. Collison, E. S. Davies,
C. D. Garner, C. I. Guindy, E. J. L. McInnes, G. McArdle,
J. McMaster, C. Wilson and J. Wolowska, Dalton Trans.,
2004, 83, 3647.
41 P. O. Lagaditis, B. Schluschaß, S. Demeshko, C. Würtele
and S. Schneider, Inorg. Chem., 2016, 55, 4529–4536.
42 M. A. García-Monforte, I. Ara, A. Martín, B. Menjón,
M. Tomás, P. J. Alonso, A. B. Arauzo, J. I. Martínez and
C. Rillo, Inorg. Chem., 2014, 53, 12384–12395.
43 E. D. McKenzie and J. M. Worthington, Inorg. Chim. Acta,
1976, 16, 9–15.
This journal is © The Royal Society of Chemistry 2017

Dalton Transactions
44 L. Yang, D. R. Powell and R. P. Houser, Dalton Trans., 2007,
96, 955–964.
45 F. N. Penkert, T. Weyhermüller, E. Bill, P. Hildebrandt,
S. Lecomte and K. Wieghardt, J. Am. Chem. Soc., 2000, 122,
9663–9673.
46 R. E. Cowley, R. P. Bontchev, J. Sorrell, O. Sarracino,
Y. Feng, H. Wang and J. M. Smith, J. Am. Chem. Soc., 2007,
129, 2424–2425.
Published on 02 November 2017. Downloaded by Universitat de Barcelona on 8/27/2020 5:18:33 PM.
47 S. Fortier, J. J. Le Roy, C. H. Chen, V. Vieru, M. Murugesu,
L. F. Chibotaru, D. J. Mindiola and K. G. Caulton, J. Am.
Chem. Soc., 2013, 135, 14670–14678.
48 C. Y. Lin, J. C. Fettinger, F. Grandjean, G. J. Long and
P. P. Power, Inorg. Chem., 2014, 53, 9400–9406.
49 M. J. Ingleson, M. Pink, H. Fan and K. G. Caulton, Inorg.
Chem., 2007, 46, 10321–10334.
50 J. Du, L. Wang, M. Xie and L. Deng, Angew. Chem., Int. Ed.,
2015, 54, 12640–12644.
51 L. Zhang, Y. Liu and L. Deng, J. Am. Chem. Soc., 2014, 136,
1–26.
52 X.-N. Yao, J.-Z. Du, Y.-Q. Zhang, X.-B. Leng, M.-W. Yang,
S.-D. Jiang, Z.-X. Wang, Z.-W. Ouyang, L. Deng, B.-W. Wang
and S. Gao, J. Am. Chem. Soc., 2017, 139, 373–380.
This journal is © The Royal Society of Chemistry 2017
View Article Online
Paper
53 X. Hu and K. Meyer, J. Am. Chem. Soc., 2004, 126, 16322–
16323.
54 C. N. Verani, S. Gallert, E. Bill, T. Weyhermüller,
K. Wieghardt and P. Chaudhuri, Chem. Commun., 1999, 38,
1747–1748.
55 G. M. Zats, H. Arora, R. Lavi, D. Yufit and L. Benisvy,
Dalton Trans., 2011, 40, 10889–10896.
56 C. Bergquist, T. Fillebeen, M. M. Morlok and G. Parkin,
J. Am. Chem. Soc., 2003, 125, 6189–6199.
57 L. Chiang, L. E. N. Allan, J. Alcantara, M. C. P. Wang, T. Storr
and M. P. Shaver, Dalton Trans., 2014, 43, 4295–4304.
58 Bruker AXS, APEX2, SAINT, SADABS, Madison, Wisconsin,
USA, 2007.
59 L. J. Farrugia, J. Appl. Crystallogr., 2012, 45, 849–854.
60 O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard
and H. Puschmann, J. Appl. Crystallogr., 2009, 42, 339–341.
61 G. M. Sheldrick, Acta Crystallogr., Sect. A: Found.
Crystallogr., 1990, 46, 467–473.
62 G. M. Sheldrick, Acta Crystallogr., Sect. C: Struct. Chem.,
2015, 71, 3–8.
63 G. M. Sheldrick, Acta Crystallogr., Sect. A: Found.
Crystallogr., 2008, 64, 112–122.
Dalton Trans., 2017, 46, 16228–16235 | 16235