Catalytic reduction of dinitrogen to tris(trimethylsilyl)amine using rhodium complexes with a pyrrole-based PNP-type pincer ligand

Article abstract of DOI:10.1039/c9cc06896a

Rhodium complexes bearing an anionic pyrrole-based PNP-type pincer ligand are synthesised and found to work as effective catalysts for the transformation of molecular dinitrogen into tris(trimethylsilyl)amine under mild reaction conditions. This is the first successful example of rhodium-catalysed dinitrogen reduction under mild reaction conditions.

Full text of DOI:10.1039/c9cc06896a

Volume 55 Number 99 25 December 2019 Pages 14859–15008
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Kazunari Yoshizawa, Yoshiaki Nishibayashi et al.
Catalytic reduction of dinitrogen to tris(trimethylsilyl)amine
using rhodium complexes with a pyrrole-based PNP-type
pincer ligand

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Catalytic reduction of dinitrogen to
tris(trimethylsilyl)amine using rhodium complexes
with a pyrrole-based PNP-type pincer ligand†
Cite this: Chem. Commun., 2019,
55, 14886
Received 4th September 2019,
Accepted 1st November 2019
a
Ryosuke Kawakami,a Shogo Kuriyama,
Hiromasa Tanaka,b Kazuya Arashiba,a
Asuka Konomi,c Kazunari Nakajima,
Kazunari Yoshizawa *c and
d
a
DOI: 10.1039/c9cc06896a
Yoshiaki Nishibayashi
*
rsc.li/chemcomm
Rhodium complexes bearing an anionic pyrrole-based PNP-type because the activation of dinitrogen by these metals is often too
pincer ligand are synthesised and found to work as effective catalysts for weak to be functionalised into ammonia and its equivalents
the transformation of molecular dinitrogen into tris(trimethylsilyl)amine such as N(SiMe3)3. Although more than 30 examples of rhodium-
under mild reaction conditions. This is the first successful example of dinitrogen complexes have been synthesised until now,17c no
rhodium-catalysed dinitrogen reduction under mild reaction conditions. successful example of the transformation of the coordinated
dinitrogen on the rhodium atom of the rhodium-dinitrogen
Various transition metal-dinitrogen complexes have been intensively complexes has yet been reported not only in a catalytic fashion
studied over the last few decades to achieve efficient catalytic but also in a stoichiometric fashion, to the best of our knowledge.
nitrogen fixation under mild reaction conditions. In 2003, Yandulov
Recently, we have found that vanadium-,3 iron-,5g and cobalt7
and Schrock reported the first example of catalytic ammonia -dinitrogen complexes bearing an anionic pyrrole-based pincer
formation from dinitrogen using a molybdenum dinitrogen ligand (PNP = 2,5-bis(di-tert-butylphosphinomethyl)pyrrolide)
complex.1 Since this pioneering report, titanium-,2 vanadium-,3 worked as effective catalysts for the formation of ammonia
molybdenum-,4 iron-,5 ruthenium-,6 osmium-,6 and cobalt7 and hydrazine in the reaction of dinitrogen gas at atmospheric
-catalysed reductions of dinitrogen to ammonia and hydrazine pressure with reductants and proton sources at ꢀ78 1C. Based
have been reported by us and other groups.8 In addition, catalytic on these research backgrounds, we newly designed rhodium-
transformation of dinitrogen into tris(trialkylsilyl)amines, which dinitrogen complexes bearing the same PNP ligand to investigate
are easily converted into ammonia by acid hydrolysis, has been their catalytic activity toward the formation of ammonia and
developed since the first report by Shiina in 19729 as an alternative N(SiMe3)3.‡ As a result, we found that the synthesized rhodium
nitrogen fixation route.10 Up to now, titanium-,11 vanadium-,12 complex worked as an effective catalyst for the formation of
chromium-,13 molybdenum-,14 tungsten-,14b iron-,15 and cobalt- N(SiMe3)3 as the first example of the rhodium-catalysed trans-
complexes16 have been used as catalysts for the formation of formation of dinitrogen under mild reaction conditions. Herein,
tris(trimethylsilyl)amine (N(SiMe3)3) under mild reaction conditions. we report preliminary results.
In sharp contrast to the intensive study of the catalytic
The reaction of [RhCl3(MeCN)3] with 1 equiv. of lithium
activity of early-to-mid transition metal-dinitrogen complexes 2,5-bis(di-tert-butylphosphinomethyl)pyrrolide (PNP-Li) and
toward nitrogen fixation, the catalytic reactivity of group 9–11 KC8 in THF at ꢀ30 1C for 1 min and then at room temperature
transition metal-dinitrogen complexes toward nitrogen fixation for 4 h gave a rhodium(II)-chloride complex bearing the PNP
has been less explored except for cobalt-dinitrogen complexes,17 ligand [RhCl(PNP)] (1) in 32% yield (Scheme 1). Isolation of
mononuclear rhodium(II) complexes is relatively limited and
rare because Rh(II) species are prone to disproportionation or
a Department of Systems Innovation, and School of Engineering, The University of Tokyo,
dimerization.18,19 The molecular structure of 1 was confirmed
Hongo, Bunkyo-ku, Tokyo 113-8656, Japan. E-mail: ynishiba@sys.t.u-tokyo.ac.jp
b School of Liberal Arts and Science, Daido University, Minami-ku,
by X-ray analysis. An ORTEP drawing is shown in Fig. 1(a).
Complex 1 has a distorted square planar geometry around the
rhodium centre. Rhodium(II) complex 1 is paramagnetic with a
solution magnetic moment of 2.0 mB at 298 K. The measured
magnetic moment is close to the spin-only value for an S = 1/2
spin state. The cyclic voltammogram (CV) of 1 in THF with
NBu4PF6 as supporting electrolyte under an atmospheric pressure
of dinitrogen or argon shows a reversible reduction wave at
Nagoya 457-8530, Japan
c Institute for Materials Chemistry and Engineering, Kyushu University, Nishi-ku,
Fukuoka 819-0395, Japan. E-mail: kazunari@ms.ifoc.kyushu-u.ac.jp
d Frontier Research Center for Energy and Resources, School of Engineering,
The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
† Electronic supplementary information (ESI) available. CCDC 1950030–1950033.
For ESI and crystallographic data in CIF or other electronic format see DOI:
10.1039/c9cc06896a
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We investigated the cation exchange of 2 with Na+ to
eliminate the Cl anion as NaCl. The reaction of 2 with 1 equiv.
of NaBAr4 (ArF = 3,5-bis(trifluoromethyl)phenyl) in THF at
F
room temperature for 20 h under an atmospheric pressure of
dinitrogen afforded the corresponding rhodium(I)-dinitrogen
complex 3 in 66% yield. Separately, 3 was obtained in 61% NMR
yield by reduction of 1 with 1 equiv. of Na–Hg in THF at room
temperature for 20 h under an atmospheric pressure of dinitro-
gen. The molecular structure of 3 shows that the rhodium atom
of 3 adopts a distorted square planar structure with an end-on
dinitrogen ligand (Fig. 1(c)). The IR spectra of 3 in solid (KBr)
and solution (THF or C6D6) states exhibit strong nNN bands at
2110 and 2112 cmꢀ1, respectively, which are assigned as the
terminal dinitrogen ligand. The nNN values of 3 are comparable
to those of previously reported Rh(I)-dinitrogen complexes.17c
A larger nNN value of 3 than the cobalt-analogue complex
[Co(N2)(PNP)]7 (2017 cmꢀ1 in THF) indicates weaker activation
of the dinitrogen ligand in 3. The CV spectrum of 3 in THF
shows no reduction wave within the solvent window.
We performed DFT calculations to get more information
on 3. The optimized structure of 3 and its selected geometric
parameters are presented in Fig. S6 (ESI†). The calculated nNN
value of the singlet state of 3 in the gas phase, 2128 cmꢀ1, is
very close to the experimental values. The bond dissociation
free energy of the Rh–N2 bond (23.3 kcal molꢀ1) of 3 is
comparable with that of the Co–N2 bond of the cobalt-
analogue complex [Co(N2)(PNP)]7 (21.3 kcal molꢀ1). On the other
Scheme 1 Synthesis of rhodium complexes bearing a pyrrole-based
anionic PNP-type pincer ligand.
hand, the electron affinity of 3 is calculated to be 21.0 kcal molꢀ1
,
which is much smaller than those calculated for [Fe(N2)(PNP)]5g
(28.6 kcal molꢀ1) and [Co(N2)(PNP)]7 (29.4 kcal molꢀ1). The smaller
electron affinity value of 3 could be consistent with the experi-
mental fact that no reduction wave was observed in the CV
measurement.
The reaction of [RhCl(CO)2]2 with 1 equiv. of PNP-Li in
toluene at room temperature for 13 h afforded a carbonyl
complex [Rh(CO)(PNP)] (4) in 42% yield. The single-crystal
X-ray analysis of 4 (Fig. 1(d)) reveals that the metrical parameters
of 4 are comparable to those of 3. The IR spectrum (KBr) of 4
shows a strong absorption of CO at 1941 cmꢀ1
.
We investigated the stoichiometric reaction of 3 toward the
formation of ammonia. Protonation of 3 with sulfuric acid in
THF afforded neither ammonia nor hydrazine. Next, the catalytic
formation of ammonia from the reaction of dinitrogen with reduc-
tants and proton sources was carried out by using 3 as a catalyst
under the reported conditions (Table S1, ESI†).4,5a However, no
Fig. 1 ORTEP drawings of 1 (a), 20ꢁ(thf)2 (b), 3 (c), and 4 (d). Thermal ellipsoids
are shown at the 50% level. Hydrogen atoms are omitted for clarity.
E1/2 = ꢀ1.36 V vs. ferrocene0/+ (Fig. S1, ESI†). The chemical formation of ammonia and hydrazine was observed under these
reduction of 1 with 1.1 equiv. of KC8 under an atmospheric reaction conditions, where only the formation of dihydrogen was
pressure of dinitrogen did not afford the corresponding observed in all cases (Table S1, ESI†). This result is in sharp contrast
rhodium(I)-dinitrogen complex but an anionic rhodium(I)- to our previous result that iron- and cobalt-dinitrogen complexes
chloride complex (K[RhCl(PNP)]) (2) in 66% yield. The formation [M(N2)(PNP)] (M = Fe and Co) worked as effective catalysts toward
of 2 was confirmed by treating 2 with 18-crown-6 in THF to afford the formation of ammonia and hydrazine.5g,7 In the iron-catalysed
[K(18-crown-6)][RhCl(PNP)] (20), which was characterized as THF- reaction,5g we proposed a reaction pathway where an anionic
adduct 20ꢁ(thf)2 by X-ray analysis (Fig. 1(b)). Rh(I) complex 20ꢁ(thf)2 Fe(0)-dinitrogen complex, which is prepared by one-electron
has longer Rh–Cl and Rh–N bonds (2.4143(6) and 2.004(2) Å) than reduction of [Fe(N2)(PNP)], plays a key reactive intermediate to
1 (2.3218(8) and 1.952(2) Å), respectively, while the mean Rh–P form a nitrogen–hydrogen bond at the terminal nitrogen atom
distance of 20ꢁ(thf)2 (2.271 Å) is shorter than that of 1 (2.322 Å).
of the coordinated dinitrogen ligand. We consider that protonation
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may not occur on the dinitrogen ligand but on the rhodium atom in of N(SiMe3)3 from dinitrogen dramatically increased at a low
3 to generate dihydrogen.20
temperature such as ꢀ40 1C because the dinitrogen ligand binding
Next, we investigated the catalytic formation of N(SiMe3)3 to the metal becomes favourable at low temperature. Based on this
from dinitrogen. Typical results are shown in Table 1. We carried previous result, we carried out the catalytic reaction at lower
out the reaction of atmospheric pressure of dinitrogen with KC8 temperature using 3 as a catalyst. As the reaction temperature
(600 equiv. to 3) as a reductant and Me3SiCl (600 equiv. to 3) as a was decreased, the produced amount of ammonia increased
silylating reagent in THF at room temperature for 20 h to afford gradually to 23.2 equiv. based on the rhodium atom at ꢀ40 1C
N(SiMe3)3, which was quantified as ammonia after acid hydro- (Table 1, entries 10–13).§ In this case, the formation of 23.9 equiv.
lysis of the reaction mixture. This reaction gave 6.8 equiv. of of N(SiMe3)3 was observed based on the rhodium atom of the
ammonia based on 3 (Table 1, entry 1). Separately, we confirmed catalyst (12% yield based on Me3SiCl), together with Me3SiSiMe3
the formation of 6.2 equiv. of N(SiMe3)3 (3% yield based on (36% yield), C4H9OSiMe3 (o1% yield), and Me3SiC4H8OSiMe3
Me3SiCl) by GC, together with Me3SiSiMe3 (7% yield), C4H9OSiMe3 (8% yield). However, the catalytic activity of 3 substantially
(3% yield), and Me3SiC4H8OSiMe3 (34% yield). After the catalytic decreased when the reaction was carried out at a further low
run, we reloaded fresh KC8 (600 equiv.) and Me3SiCl (600 equiv.) temperature such as ꢀ50 or ꢀ60 1C (Table 1, entries 14 and 15).
and stirred the reaction mixture at room temperature for another
We have not yet clarified the reaction mechanism of the
20 h under 1 atm of N2. However, the obtained amount of ammonia catalytic silylation of dinitrogen using 3 as a catalyst. As proposed
did not increase. This result indicates that the rhodium catalyst is in a previous study,10 we consider that the present reaction
no longer active after a catalytic run. Use of Na as a reductant proceeds homogeneously via a Me3Si radical, which is generated
instead of KC8 afforded no N(SiMe3)3 (Table S2, ESI†). We also in situ from Me3SiCl and KC8, as an active silylating reagent. In
examined other solvents such as Et2O, DME, and toluene, but THF fact, no inhibition of the formation of N(SiMe3)3 in the presence
was the best solvent in the present reaction system (Table S3, ESI†). of Hg was observed in the present reaction system, indicating
When rhodium complexes 1, 2, and 4 as well as a rhodium- that homogeneous rhodium complexes may work as reactive
ethylene complex [Rh(CH2CH2)(PNP)], which was independently species for the silylation of dinitrogen.22
reported by Yamashita and co-workers,21 were used as catalysts
Reactions of 3 with three Me3Si radicals to yield [Rh(PNP)-
in place of 3, lower amounts of ammonia were obtained based (NN(SiMe3)x)] (x = 1–3) were evaluated by DFT calculations. We
on the rhodium atom (Table 1, entries 2–5). Then, we employed found that the Rh(PNP) framework can accept up to three SiMe3
commercially available simple rhodium complexes as catalysts radicals due to the bulkiness of the SiMe3 group. The optimized
(Table 1, entries 6–9), but these rhodium complexes worked less structures of the silylated complexes [Rh(PNP)(NN(SiMe3)x)]
effectively than 3.
(x = 1–3) are presented in Fig. S7 (ESI†). Rh(I), Rh(II) and Rh(III)
Masuda and co-workers16d previously reported that the states are involved as intermediates. The free energy changes
catalytic activity of their cobalt complex toward the formation (DG298) for the three successive addition of the SiMe3 radical to 3
are calculated to be +1.9 kcal molꢀ1 (x = 1), ꢀ17.9 kcal molꢀ1
(x = 2), and ꢀ0.2 kcal molꢀ1 (x = 3). Although the steps in which
the Rh(II) species are formed are less favourable, the calculated
DG298 values indicate that the silylation reactions of 3 with three
Me3Si radicals to [Rh(PNP)(NN(SiMe3)3)] can totally proceed from a
thermodynamic point of view.
Table 1 Catalytic reduction of dinitrogen to tris(trimethylsilyl)amine using
rhodium complexesa
In summary, we have found that the newly designed and
prepared rhodium dinitrogen complex bearing an anionic pyrrole-
based PNP-type pincer ligand worked as an effective catalyst for
the silylation of dinitrogen under mild reaction conditions,
where up to 23 equiv. of N(SiMe3)3 were produced based on the
rhodium atom of the catalyst. This result demonstrates the first
successful example of the rhodium-catalysed-nitrogen fixation
under mild reaction conditions. One of the possible roles of
the PNP pincer ligand is to stabilize various oxidation
states during the catalytic reaction. We hope that the finding
described in the present paper provides a valuable suggestion
to develop late transition metal-catalysed nitrogen fixation
under mild reaction conditions. Further studies are ongoing
in our laboratory to develop novel transition-metal catalysts for
nitrogen fixation.
Entry
Catalyst
T
NH3 (equiv.)b
1
2
3
4
5
6
7
8
3
1
2
4
rt
rt
rt
rt
rt
rt
rt
rt
6.8 ꢂ 0.7c (6.2d)
3.9
5.4
2.2
5.3
3.5
2.2
2.8
0.1
6.2
[Rh(CH2CH2)(PNP)]
[RhCl(CO)(PPh3)2]
[RhCl(PPh3)3]
[Rh2(OAc)2]
9
[Rh4(CO)12
]
rt
10
11
12
13
14
15
3
3
3
3
3
3
0 1C
ꢀ20 1C
ꢀ30 1C
ꢀ40 1C
ꢀ50 1C
ꢀ60 1C
7.4
17.3
23.2 ꢂ 0.3c (23.9d)
12.3
7.3
a
A mixture of the rhodium complex (0.0025 mmol/Rh), KC8 (1.5 mmol),
and Me3SiCl (1.5 mmol) in THF (3.0 mL) was stirred at room tempera-
The present project was supported by CREST, JST (Grant
JPMJCR1541). We acknowledge Grants-in-Aid for Scientific Research
(Grants JP17H01201, JP15H05798, JP18K19093, JP18K05148, and
JP19K23645) from JSPS and MEXT.
b
ture for 20 h under 1 atm of N2. Equiv. of ammonia based on the Rh
atom of the catalyst after acid hydrolysis of the reaction mixture.
c
d
Averages of triplicate runs are shown. GC yield of N(SiMe3)3.
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Conflicts of interest
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There are no conflicts to declare.
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‡ Yamashita and co-workers independently reported rhodium–ethylene
and –dihydrogen complexes bearing the same PNP ligand. See ref. 21.
§ When [RhCl(CO)(PPh3)2] was used as a catalyst for dinitrogen silylation at
ꢀ40 1C, 11.0 equiv. of ammonia based on the rhodium atom were
produced after hydrolysis. This result indicates that the catalytic activity
of [RhCl(CO)(PPh3)2] was higher than that at room temperature (see
Table 1, entry 6).
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