Dinitrogen activation by a penta-pyridyl molybdenum complex

Article abstract of DOI:10.1039/d0dt02692a

A new dinitrogen (N2) molybdenum(0) complex supported exclusively by pyridine ligands was synthesized. The X-ray crystal structure of the complex elucidated the activated nature of the N2 ligand, consistent with a low N-N IR stretching frequency. Natural bond orbital (NBO) analyses on this system confirmed a strong π-backdonation arising from the large p orbital character in molybdenum lone pairs. The protonation of the N2 ligand using decamethyl chromocene (CrCp?2) in the presence of lutidinium salt afforded 1.22 equivalents of ammonia (NH3).

Full text of DOI:10.1039/d0dt02692a

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Dinitrogen activation by penta-pyridyl molybdenum complex
Jeongmin Cha,a Hyunchul Kwon,a Hayoung Song,a and Eunsung Lee*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A
new dinitrogen (N2) molybdenum(0) complex supported
iPr
exclusively by pyridine ligands was synthesized. The X-ray crystal
structure of the complex elucidated the activated nature of N2
ligand, consistent with the low N‒N IR stretching frequency.
Natural bond orbital (NBO) analyses on this system confirmed
strong π-backdonation derived by large p orbital character in
molybdenum lone pairs. The protonation of N2 ligand using
decamethyl chromocene (CrCp*2) in presence of a lutidinium salt
afforded 1.22 equivalents of ammonia (NH3).
a
c
b
BArF
4
Cl
iPr
PiPr2
PiPr2
iPr
iPr
P
iPr2P
Fe
B
HIPT
N
N
Mo
Cl
N
N
N
Mo
N
HIPT
iPr
HIPT
P
Cl
N
iPr
Figure 1 Representative examples of the catalysts for the N2 reduction. a) reports by
Schrock group,8 b) reports by Peters group,9 c) reports by Nishibayashi group.10
Nitrogen is an essential element for organisms to sustain their
biological functions.1 One of the abundant and easily accessible
nitrogen sources is N2 in the atmosphere. However, due to the
inertness of N2, its conversion to valuable compounds such as
NH3 is challenging.2,3 The Haber-Bosch process has been used to
convert N2 to NH3 using hydrogen gas (H2) as an H atom source.
However, this process has limitations associated with energy
consumption and environmental issues.4
The first reported transition metal complex with N2 as a ligand
was synthesized with ruthenium as the metal center.5 Although
it has been shown that various transition metals could activate
N2, iron and molybdenum have been mostly employed for this
purpose because they are the components of the FeMo
cofactor, the most studied active site of nitrogenase enzymes.6
Chatt and Hidai showed N2 functionalization using molybdenum
or tungsten complexes.7 The catalytic synthesis of NH3 by a
transition metal complex under ambient condition was first
reported by Schrock and Yandulov (Figure 1a) who also
characterized the eight key intermediates.8 The Peters group
has shown that with their iron system (Figure 1b) it was possible
to catalyse the N2 to NH3 reduction.9 Most recently, the highest
catalytic turnover (103 units) was achieved by the Nishibayashi
group, whose system yielded 4350 equivalent of NH3 per
catalyst (Figure 1c).10 More recently, functionalization of N2
complexes such as protonation, sillyation, and borylation has
been successfully demonstrated.11
Although the N2 chemistry using transition metal (TM)
complexes has been thriving since the 20th century, low valent
TM-N2 complexes usually bear phosphines as their ancillary
ligand. The soft nature of the phosphorous atom, which is well-
matched with soft low valent metals, and the strong donating
property of the phosphine ligands makes the metal center more
electron-rich resulting in sufficient π-backdonation to N2
ligand.12 L-type nitrogen donors such as tertiary amines, imines,
and pyridines are classified as slightly weaker sigma-donating
ligands than the phosphines.13 Although various low valent TM-
N2 complexes bearing the nitrogen donors have been reported,
most of the nitrogen donor have been utilized as a part of the
chelating ligands.10b, 11g, 11h, 14 The low valent TM-N2 complexes
bearing exclusively nitrogen donors are relatively rare and
commonly based on pyridine-diimine or tris(pyrazolyl)borate.15
Herein, we report a Mo(0)-N2 complex supported by a penta-
pyridyl ligand.
Reduction of the known complex 116 with potassium graphite
(KC8) in THF afforded blue complex 2 (Scheme 1). 1H NMR
spectrum of 2 showed a complex adopting C2v symmetry (Figure
S1). The IR data obtained from a thin film formed by
evaporation of THF solution on KBr window surface indicated
activation of the N2 ligand (1847 cm-1, Figure2b, black spectrum).
a. Department of Chemistry, Pohang University of Science and Technology, 77
Cheongam-Ro, 37673 Pohang, Republic of Korea.
b. Division of Advanced Materials Science, Pohang University of Science and
Technology, 77 Cheongam-Ro, 37673, Pohang, Republic of Korea.
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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DOI: 10.1039/D0DT02692A
2I-
N
N
N
N
I
50 equiv
70 equiv
LutHOTf
CrCp*2
N
N
N
N
N
N
3.05 equiv KC8
1.22 equiv NH3
per catalyst
Mo
N
Mo
N
Mo
N
N
N
N
N
N
N
THF / RT
3 h
THF / RT
N2
27.8 %
Scheme 2 Synthesis of NH3 using complex 1 in presence of lutidinium salt as a proton
source decamethyl chromocene (CrCp*2)as an electron source. Yield was measured by
indophenol method.
2
1
Scheme 1 Synthesis of the dinitrogen complex 2 and IR stretching frequencies of the N2
ligand.
(5.2 eq), other compounds were formed as major portions. We
could isolate one of the compounds by independent synthesis.
Exposing 1 under the excess amount of sodium and extracting
the resulting mixture with diethyl ether afforded the compound
(3) (Figure S7). Cooling 3 in dimethoxy ethane formed rod shape
crystals. However, the poor crystal quality of 3 provides only
connectivity information of 3 by X-ray crystallography analysis
(Figure S8). To our surprise, the crystal structure of 3 was
revealed that the ligand lost two equatorial pyridines and
formed a polymeric sodium amide complex. Considering these
results, we assume that the inhomogeneity (1 and KC8 are
insoluble in THF) of the large scale reaction and further
Figure 2 a) Solid-state structure of 2 as determined using X-ray crystallography. The
thermal ellipsoids are shown at the 25% probability level. Selected bond lengths (Å)
(computed bond lengths by DFT) and angles (°) for 2: Mo1-N6 1.942(6) (1.959), N6-N7
1.142(10) (1.133), Mo1-N1 2.122 (2.120), Mo1-N2 2.122 (2.118), Mo1-N3 2.122 (2.117), reduction of 2 would interfere with the successful large scale
Mo1-N4 2.121(3) (2.120), Mo1-N5 2.096(6) (2.115), Mo1-N6-N7 180.00 (179.97), N5-
Mo1-N6 180.00 (179.97) b) IR spectrum of 2 (15N2, red) and 2 (14N2, black).
synthesis. Nevertheless, this result shows that the choice of
auxiliary ligands and proton sources is very important for the
successful reduction of N2 in the presence of strong reduction
This N-N stretching is more red shifted than the common
conditions. This is further supported by a recent report by the
stretching in neutral N2 complexes (1900 – 2100 cm-1).2-3, 7a-c, 12b,
Liddle group, which addresses that N-based acids undergo
12c, 17
Similar degree of N2 activation in Mo(0) systems (N‒N
reduction by KC8 leading to the formation of NH3.18
stretching frequencies: 1836, 1838 cm-1) were achieved by
complexes supported by N-heterocyclic carbene ligands.11a To
confirm the coordination of the dinitrogen ligand, 15N2 enriched
2 was synthesized. IR spectra of the compound showed 15N2
stretching at 1775 cm-1 (Figure 2b, red spectrum). The single
crystals of 2 were obtained by keeping a solution (Et2O:THF=1:1
by volume) of 2 at -40 °C in a freezer. The X-ray crystal structure
of 2 also indicated the activated nature of the N2 molecule, with
Given the strong activation of the N2 ligand in 2, we utilized
NBO analyses on this system compared with the known
complex, (PMe3)5MoN2 (4)19 that has five identical dative donor
(PMe3) and zero-valent Mo center (Table 1, see ESI for detailed
information). The donor-acceptor interactions in the complexes
were investigated with second-order perturbation analyses. We
noticed that both of the complexes have strong interaction
between lone pairs of Mo and antibonding pairs of N2 that
contributes to the traditional π-backdonation. The stabilization
energy by the interactions was much higher in 2 (331.86
kcal/mol) than in 4 (111.03 kcal/mol), which suggests the π-
backdonation is dominant in 2. We attribute this difference to
the larger p-character of Mo lone pairs of 2. The larger p
character would be a consequence of the stronger π-
interaction of pyridines with d orbitals of Mo. Indeed, the
average composition of natural atomic orbitals for Mo-N(py)
was found as p 43.78%, d 39.97%, and for Mo-P p 50.72%, d
the N‒N bond distance (1.142(10) Å) and the Mo‒Nα bond
distance (1.942(6) Å) (Figure 2a). Bond distances in the
molybdenium center were in good agreements with the values
obtained from DFT calculations (Table S2). To the best of our
knowledge, this is the first example of the structurally
characterized zero-valent TM complex supported by penta-
pyridine ligand.
Although a small scale synthesis of 2 (7 μmol) was reproducible,
the synthesis of 2 using more than a 35 mg of 1 (38 μmol),
however, was not successful because of unavoidable formation
of unidentified compounds along with 2. While investigating in
Complex
Stabilization energy
(LP(Mo) to BD*(N2))‡
ν(N2)
p character on
LP(Mo)※
a
small scale synthesis, we observed the unidentified
1847 cm-1
1950 cm-1¶
13.42 %
0.17 %
compounds were generated if KC8 was added in excess. One of
the compounds was formed as major portion using 4.5
equivalent of KC8 was used (Figure S6). The compound has C2v
symmetry like 2, and has more upfield shifted peaks than 2.
Unfortunately, all our attempts to isolate and identify the
compound were not successful due to the similar solubility with
2. When the reaction was progressed with larger amount of KC8
Py5Me2MoN2 (2)
(PMe3)5MoN2 (4)
331.86 kcal/mol
111.03 kcal/mol
‡ Average value for LP(Mo) to BD*(N2) interactions
¶ experimental value from the literature.18 ※Average value for LP(Mo)s
,
Table 1 Selected results obtained from NBO analyses. The calculation was performed
at wB97xD/def2SVP level of theory. See ESI for detailed information.
2 | J. Name., 2012, 00, 1-3
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5.
6.
7.
A. D. Allen and C. V. Senoff, Chemical CommVuinewicAarttiicolenOsnline
31.86% (See ESI for detailed information). This data is in line
with the experimental observation when comparing to the IR
wavelengths (1847 cm-1 for 2, 1950 cm-1 for 4).
Having well-defined N2 complex supported exclusively by
pyridine ligands, we envisioned the reduction of N2 ligand. The
(London), 1965, 621-622.
DOI: 10.1039/D0DT02692A
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proton and electron sources followed
a
well-known
combination reported by Schrock.8a Following the experimental
procedure9b with slight modifications, a solution of 2 in THF was
placed in a Schlenk flask and frozen in a cold well cooled by
liquid nitrogen. A THF solution containing 70 equivalents of
decamethyl chromocene (CrCp*2) and 50 equivalents of
lutidinium salt were added to the reaction vessel in portions,
and the flask was cooled again . The reaction mixture was
stirred for 3 hours at room temperature to afford 1.22
equivalents of NH3 per catalyst on average over three runs
(Scheme 2). Using cobaltocene (CoCp2) instead of the CrCp*2 led
to a decreasing yield (0.38 eq.). Operating the reaction in low
temperature ( -78 oC) also led to decreasing yield (0.29 eq. from
8.
9.
CrCp* , 0.19 eq. from CoCp2). We also confirmed the true
2
nitrogen source was N2 by using 15N2 enriched 2 as a substrate
to afford 15NH3 (Figure S10). Although the catalytic performance
of N2 reduction with 2 is not significant, this is the first example
of N2 reduction to ammonia with a transition metal complex
with exclusively by pyridine ligands.
10.
Conclusion
In conclusion, the first example of the structurally
characterized zero-valent Mo-N2 complex supported by penta-
pyridine ligand is reported. NBO analyses on this system
showed the strong π-backdonation was originated by large p
orbital character in molybdenum lone pairs. The N2 ligand in 2
could be protonated by CrCp* and [LutH]OTf to afford 1.22
2
equivalents of ammonia (NH3).
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgments
The X-ray diffraction experiment was performed at the Pohang
Accelerator Laboratory (Beamline 2D) using synchrotron
radiation. This work was supported by Institute for Basic Science
(IBS) [IBS-R007-D1] and the National Research Foundation of
Korea (NRF) (NRF-2019M1A2A2067940). The computational
resource was supported by KISTI. We thank Dr. Ewa Pietrasiak
for helpful discussion.
11.
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