Selected Paper

Development of Highly Active Ir­PNP Catalysts for Hydrogenation of

Carbon Dioxide with Organic Bases

Wataru Aoki, Natdanai Wattanavinin, Shuhei Kusumoto, and Kyoko Nozaki*

Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo,
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656
E-mail: [email protected]

Received: September 11, 2015; Accepted: October 2, 2015; Web Released: January 15, 2016

Kyoko Nozaki
Kyoko Nozaki, born in Osaka received her B.Sc. in 1986 and her Ph.D. in 1991 from Kyoto University under
the guidance of Professor Kiitiro Utimoto. During her Ph.D. study, she joined Professor Clayton H.
Heathcock’s group at the University of California at Berkeley as an exchange student. In 1991, she started
her research career as an instructor at Kyoto University, became an associate professor in 1999, and then
moved to the University of Tokyo as an associate professor in 2002. Since 2003, she is a full professor at the
University of Tokyo. Her research interest is focused on development of homogeneous catalysts for polymer
synthesis and organic synthesis.

Abstract exoergonic, by 4 kJ mol¹1, in aqueous solution (eq 2).2­6 Bases

Methoxy-substituted PNP­iridium(III) complexes and pyr- such as KOH, NaHCO3, and NR3 are therefore used to make
azine-based PNP­iridium(III) complexes were developed and the reaction thermodynamically more favourable (eq 3)2­6 and
used to hydrogenate carbon dioxide in the presence of to accelerate it kinetically.7­11 Recently, homogeneous hydro-
triethanolamine as a base. The methoxy-substituted PNP­ genation of carbon dioxide with various transition-metal cata-
hydridodichloridoiridium complex (C-HCl2) showed the high- lysts (Ir,2­6,8,12­24 Rh,2­6,14,15,25 Ru,2­6,8­11,14­16,26­38 Co,39­43
est turnover number, 160000; this is the highest value ever Fe,2­6,38,41,44­46 and others2­6,46) has been extensively studied.
reported with an organic base in an aqueous medium. The Among the catalysts developed for CO2 hydrogenation, the
reactivities of these complexes, derived from their ligand trihydridoiridium­PNP pincer complex A-H3 showed the high-
modification, were further studied. The results were as follows. est turnover number (TON) for formic acid production using
(i) The pyrazine-based PNP­trihydridoiridium complex under- KOH as the base (Scheme 2).12
goes release of dihydrogen to afford dihydridoamido complex, The use of strong bases, however, requires an additional
possibly because of easy dearomatization of the pyrazine ring. process, neutralization of the resulting formate salt with strong
This process was reversible, i.e., B-H2amido can readily be acid, to isolate formic acid; this is accompanied by forma-
converted back to B-H3 on exposure to dihydrogen. (ii) The tion of undesired inorganic salts (Scheme 1, top).11 Formic
p-methoxy-substituted dihydridochlorido complex showed fac- acid can be isolated by simple distillation from ammonium
ile disproportionation of the chloride anion on the iridium formate, therefore the development of a highly active cata-
center; this is attributed to the electron-donating nature of the lyst for hydrogenation of carbon dioxide in the presence of
methoxypyridine backbone. less volatile amine bases is desirable for industrial applica-
tions (Scheme 1, bottom).29 After several decades of intensive
research on catalysts, a significant improvement was made by
Carbon dioxide is a cheap, abundant, nontoxic, but less
reactive carbon resource, compared with carbon monoxide, one CO2 KOH HCOOK neutralization
+ +H2O
of the most widely used C1 carbon sources. Catalytic hydro- H2 HX KX
genation to produce formic acid is a promising approach to HCOOH
CO2 use, and has been intensively studied as an alternative to CO2 [HCOO] distillation
the reaction of carbon monoxide with water, which is generally + [HNR3]
used in current industrial processes.1 The reaction of carbon H2 NR3
NR3
dioxide with dihydrogen to produce formic acid is endoergonic
by 33 kJ mol¹1 in the gas phase (eq 1) and only slightly Scheme 1. Production and isolation of formic acid.

Bull. Chem. Soc. Jpn. 2016, 89, 113–124 | doi:10.1246/bcsj.20150311 © 2016 The Chemical Society of Japan | 113
 1.0 M Base aq. (5.0 mL)
CO2 (2.5 MPa) cat. A-H3 (0.010 mmol),
+ HCOO·HBase
H 2 (2.5 MPa) THF (0.1 mL), 200°C, 2 h

HH
i
Pr2P Ir PiPr2
TOF 150000 h–1 (Base: KOH)
H N
TOF 14000 h –1 (Base: triethanolamine)

A-H3

Scheme 2. CO2 hydrogenation catalyzed by A-H3.

Y Z
iPr PiPr2 iPr2P PiPr2 iPr PiPr i Pr PiPr2
2P 2P 2 2P Ir
N N N X N

N A~C-H3: X = Y= Z=H
OMe A~C-H2Cl: X = Y = H, Z = Cl
A B C A~C-HCl2 : X = H, Y = Z = Cl
C-Cl3 : X = Y = Z = Cl

Figure 1. Ligands and iridium complexes used in this study for catalytic CO2 hydrogenation.

Jessop et al.; they developed [RuCl(OAc)(PMe3)4], which dis- phinomethyl)pyridine) trihydrido complex A-H3 and di-
played a high initial turnover frequency (TOF, 95000 h¹1 in hydridochlorido complex A-H2Cl were synthesized using a
20 min) with triethylamine in supercritical carbon dioxide.35 previously reported method.12 One hydride in A-H2Cl can be
Recently, [Ru(PNP)(H)(Cl)CO] was reported to show a high replaced by a chloride anion by reaction with excess chloro-
initial TOF (1100000 h¹1 in the initial stage, TON 200000) in form at room temperature, to afford the hydridodichlorido
the presence of DBU as a base.30 Further improvement of the complex A-HCl2. All these complexes bearing pyridine-based
catalytic activity, however, remains a challenge, because the ligands (complexes A-H3­A-HCl2) were highly stable against
activities recorded with organic bases are much lower than the loss of dihydrogen and ligand disproportionation (discussed
those achieved using inorganic strong bases. For example, in the following chapter) and no changes were observed after
the high TOF (150000 h¹1 in 2 h) we recently reported with several days in tetrahydrofuran (THF) under argon at room
the trihydridoiridium complex A-H3 in the presence of KOH temperature. The pyrazine-based dihydridochlorido complex
decreased significantly when triethanolamine was used as the B-H2Cl was synthesized in four steps from commercially
base (Scheme 2).12,13 available 2,6-dimethylpyrazine (2; analogous to the procedure
In this study, we developed pyrazine-based PNP and for A-H2Cl, Schemes 3 and 4). Treatment of B-H2Cl with
methoxy-substituted PNP ligands B and C, and their iridium chloroform resulted in formation of dichlorido complex B-
complexes (Figure 1). Iridium complexes containing ligands HCl2. Although nuclear magnetic resonance (NMR) spectros-
A­C and various numbers of hydride and chloride ligands copy confirmed the formation of trihydrido complex B-H3
were examined in hydrogenation of carbon dioxide. The when B-H2Cl was treated with excess sodium hydride, B-H3
methoxy-substituted PNP­hydridodichloridoiridium (C-HCl2) was not stable and the reaction always resulted in formation of
showed the highest activity under the examined reaction con- a mixture of B-H3 and B-H2amido dihydrido complexes after
ditions using triethanolamine as the base. release of one dihydrogen molecule. Complex C-H2Cl, bear-
CO2 ðgÞ þ H2 ðgÞ ! HCOOHðlÞ ing a PNP ligand with a methoxy group, was also synthesized
Gð298KÞ ¼ 33 kJ mol1 ð1Þ from the methoxy-substituted ligand using a similar procedure
CO2 ðaqÞ þ H2 ðaqÞ ! HCOOHðaqÞ for A-H2Cl and B-H2Cl shown in Schemes 3 and 4. A-H2Cl
and B-H2Cl were stable in solution and could be isolated by
Gð298KÞ ¼ 4 kJ mol1 ð2Þ
single recrystallization, but the crystals of C-H2Cl obtained
CO2 ðaqÞ þ H2 ðaqÞ þ NH3 ðaqÞ ! HCOO=H4 NðaqÞ
by recrystallization from THF/hexane were always contami-
Gð298KÞ ¼ 35 kJ mol1 ð3Þ nated by a small amount of dichlorido complex C-HCl2. The
formation of C-HCl2 resulted from disproportionation of the
Results and Discussion dihydridochlorido complex (C-H2Cl) to afford the mono-
Synthesis of Complexes. The synthetic schemes for hydridodichlorido complex (C-HCl2) and trihydrido complex
the PNP pincer-type iridium complexes A­C-H3, A­C-H2Cl, (C-H3) on standing in solution (vide infra). The trihydrido com-
A­C-HCl2, and C-Cl3 are summarized in Schemes 3 and 4. plex C-H3 was prepared by treatment of C-H2Cl with sodium
The pyridine-based PNP ligand 1 (2,6-bis(diisopropylphos- hydride. C-H3, in contrast to B-H3, is stable against dihydro-

114 | Bull. Chem. Soc. Jpn. 2016, 89, 113–124 | doi:10.1246/bcsj.20150311 © 2016 The Chemical Society of Japan
 BH3 BH3
Cl Cl LiPiPr2 i
Pr2P Pi Pr2 i
Pr2P PiPr2
N NCS (2.3 equiv) N BH3 N morpholine
(2.3 equiv) (neat) N
BPO (0.03 equiv)
CCl4, reflux, 1 d THF,12 h
N N –78 °C to rt N 90 °C, 15 h
N
2 3 4 5
1) n BuLi (2.1 equiv) i
Pr2P PiPr2
TMEDA (2.2 equiv)
N (MeO)2SO2 (1.0 equiv) N N
K2CO3 (2.9 equiv) 2) ClPiPr 2 (2.2 equiv)
acetone, reflux, 2 h THF/hexane, 21 h
–78 °C to rt
OH OMe OMe
6 7 8

Scheme 3. Synthesis of ligands (BPO; benzoyl peroxide. NCS; N-chlorosuccinimide. TMEDA; N,N,N¤,N¤-tetramethylethylene-
diamine).

H Cl
H2 (2.5–3.0 MPa)
i i i
Pr2P P Pr2 [IrCl(coe)2]2 Pr2P Ir PiPr2
N (0.35–0.45 equiv) H N
THF, 80 °C, 7–12 h
X X
1 (X = CH) A-H2Cl (X = CH)
5 (X = N) B-H2Cl (X = N)
8 (X = C–OMe) C-H2Cl (X = C–OMe)

HH H H H
i
Pr2P Ir PiPr2 i
Pr2P Ir i
P Pr2 i
Pr2P Ir PiPr2
NaH (excess) H N H N H N
or +
THF, rt, 1 d
X N N
A-H3 (X = CH)
B-H3 B-H2amido
C-H3 (X = C–OMe)
(37 : 63)
(77 : 23 [H2, 5.0 MPa, rt, 16 h])

Cl Cl
Cl Cl
i
i C2 Cl6 (1.1 equiv) Pr2P Ir PiPr2
Pr2P Ir PiPr2
A-H2Cl Cl N
CHCl3 H N [IrCl(coe)2 ]2
B-H2Cl (0.5 equiv)
C-H2Cl 8
X THF, 65 °C, 1 d
OMe
A-HCl2 (X = CH)
B-HCl2 (X = N) C-Cl3
C-HCl2 (X = C–OMe)

Scheme 4. Synthesis of PNP-Ir(III) complexes.

gen release, even when it is exposed to reduced pressure in THF the chloride anion in B-H2Cl and hydride in A-HCl2, B-HCl2,
solution. C-H2Cl can be cleanly chlorinated by chloroform to and C-HCl2 occupy the coordination cite cis to the nitrogen.
afford the dichlorido complex C-HCl2. The trichlorido complex Comparison of Iridium Complexes. The use of different
C-Cl3 was also synthesized by the reaction of ligand 8 and an ligands, i.e., pyridine, pyrazine, and methoxypyridine, resulted
iridium precursor in the presence of a chlorine source, hexa- in significant changes in the structures and spectroscopic param-
chloroethane. The structures of all these complexes were deter- eters of the iridium complexes. The X-ray structures, spectro-
mined using 1H, 31P, and 13C NMR, spectroscopies, infrared scopic parameters, and calculated natural atomic charges for
(IR) spectroscopy, and electron-spray ionization mass spec- complexes A-HCl2, B-HCl2, and C-HCl2 are shown in Table 1.
trometry (See the next section and Supplementary Information). Regardless of the number of chloride anions on the iridium
The structures of B-H2Cl, A-HCl2, B-HCl2, and C-HCl2 were centre, the hydride signals of the pyrazine-based complexes B-
elucidated by X-ray single-crystal analysis, which revealed that H3 (¹10.08 and ¹18.95 ppm), B-H2Cl (¹17.77 and ¹21.37

Bull. Chem. Soc. Jpn. 2016, 89, 113–124 | doi:10.1246/bcsj.20150311 © 2016 The Chemical Society of Japan | 115
 Table 1. Crystal structures, observed parameters, calculated data, and catalytic activity for A-HCl2,
B-HCl2, and C-HCl2

A-HCl2 B-HCl2 C-HCl2

Crystal structurea)

Hydride in 1H NMR/ppm ¹21.81 ¹20.44 ¹22.50

Ir­H vibration in IR/cm¹1 2204 2214 2197
Natural atomic ¹0.71690 ¹0.71607 ¹0.71709
charge of Irb)
Natural atomic 0.12037 0.12496 0.11946
charge of hydrideb)
TON for hydrogenation 12000 8100 38000
of CO2c)
a) Thermal ellipsoids are drawn with 50% probability. Hydrogens on carbon atoms and solvents are
omitted for clarity. Detailed information is available in the Supporting Information. b) Hybrid functional
B3LYP11 and Lanl2dz12 on iridium, and 6-31++G(d,p) on other atoms were used as basis sets for the
calculations. c) Turnover number for hydrogenation of CO2 in one hour (corresponding to the data in
Figure 4, blue bars).

ppm), and B-HCl2 (¹20.44 ppm) were observed at significantly presence of two hydrides on the iridium. The signals were
lower field compared with those for the corresponding pyridine- assigned to B-H2amido, by comparison with the reported data
based complexes A-H3 (¹10.31 and ¹20.22 ppm), A-H2Cl for the dihydridoamido complex A-H2amido.12 After standing
(¹18.85 and ¹22.18 ppm), and A-HCl2 (¹21.81 ppm). In con- in a dihydrogen atmosphere at room temperature for 12 h, the
trast, the hydride signals for the p-methoxy-substituted PNP intensities of the 31P NMR signal at 41 ppm and the hydride
complexes C-H3 (¹10.47 and ¹20.53 ppm), C-H2Cl (¹19.05 signals at ¹16.7 and ¹22.5 ppm decreased, accompanied by the
and ¹22.57 ppm), and C-HCl2 (¹22.50 ppm) were observed at appearance of signals corresponding to B-H3 (Figure 2(ii)), and
slightly higher field than those for A-H3 (¹10.31and ¹20.22 the intensities of the signals for B-H2amido decreased to 20%
ppm), A-H2Cl (¹18.85 and ¹22.18 ppm), and A-HCl2 (¹21.81 of the original level after further 11 h at 55 °C (Figure 2(iii)).
ppm). The IR absorbance of the Ir­H vibration in A-HCl2, B- This dihydrogen addition was reversible since B-H3 was cleanly
HCl2, and C-HCl2 showed the same trend as the hydride converted back to B-H2amido at 80 °C after 28 h in an argon
signals, i.e., the wavenumber for C-HCl2 (2197 cm¹1) was atmosphere in THF solution (Figures 2(iii)­2(v)). Similar di-
lower than those for A-HCl2 (2204 cm¹1) and B-HCl2 (2214 hydrogen addition was also observed with A-H2amido, but the
cm¹1); this indicates that the Ir­H bonding energy in C-HCl2 resulting trihydrido complex A-H3 was stable against dihydro-
was the lowest. Differences among the electronic characters gen release even at reduced pressure.12 This facile dihydrogen
were also investigated theoretically, using density functional release from trihydrido complex B-H3, which sharply con-
theory (DFT) calculations.47­52 In natural population analysis, trasts with the stability of the corresponding A-H3 and C-H3
the natural atomic charge on the iridium centre in B-HCl2 complexes, even under vacuum in solution, is attributed to the
(¹0.71607) was less negative than that in A-HCl2 (¹0.71690). lower aromaticity of pyrazine compared to those of pyridine
The higher electron population on the iridium and larger and methoxypyridine.53 Although the dihydridochlorido com-
negative charge on the hydride in C-HCl2 (¹0.71709 and plexes A-H2Cl and B-H2Cl were isolated in their pure forms by
0.11946, respectively) are consistent with the electron-donating recrystallization, C-H2Cl could only be isolated by repeated,
ability of methoxypyridine. usually three times, recrystallization, resulting in a low yield. To
Characteristic Behaviours of Complexes B-H2amido and elucidate the different behaviour of C-H2Cl, the precipitates and
C-H2Cl in Solution. During the preparation of the complexes, mother liquids were carefully analysed using 1H and 31P NMR
we observed two characteristic behaviours, as briefly described spectroscopies (Figure 3). Recrystallization from THF/pentane
in the previous section. Representative results are summarized solution gave crystals of C-H2Cl contaminated with a small
in Figures 2 and 3. Complex B-H2amido underwent facile amount of hydridodichlorido complex C-HCl2 (Figure 3(ii)).
dihydrogen addition on exposure to a dihydrogen atmos- In addition to the original dihydridochlorido complex C-H2Cl,
phere in C6D6. The 31P and 1H NMR spectra and the reaction the hydridodichlorido complex C-HCl2 and trihydrido complex
are shown in Figure 2. The signals at 41 ppm in the 31P NMR C-H3 were observed in the mother liquid (Figure 3(iii)). This
spectrum, and ¹16.7 and ¹22.5 ppm in the 1H NMR spectrum facile disproportionation can be attributed to the strong electron-
(Figure 2(i)) indicate an unsymmetrical PNP structure and the donating ability of the methoxypyridine ligand,54­56 that is, the

116 | Bull. Chem. Soc. Jpn. 2016, 89, 113–124 | doi:10.1246/bcsj.20150311 © 2016 The Chemical Society of Japan
 H HH
i
Pr2 P Ir PiPr2 i
Pr2P Ir PiPr 2
H THF 1 atm H 2 1 atm H2 H
N N
rt, 12 h 55 °C, 11 h
31 1 31
N P, H NMR P, 1 H NMR 31
P, 1H NMR N
B-H2 amido (i) (ii) (iii) B-H3

H
i
degassed H2 degassed H2 Pr 2P Ir PiPr 2
H
55 °C, 12 h 80 °C, 28 h N

31
P, 1H NMR 31
P, 1 H NMR
N
(iv) (v) B-H2amido

Figure 2. Interconversion of B-H2amido and B-H3 in C6D6, monitored by 1H NMR (hydride region, left) and 31
P NMR
(right) spectroscopies.

methoxypyridine moiety facilitates the formation of a cationic catalytic activity of this catalytic hydrogenation system. This
intermediate, with release of one anionic ligand, providing an would be the result of stabilization of the cationic intermediates
intermediate for disproportionation of anions on the iridium C-b and C-d in the proposed catalytic cycle (Scheme 5), as
centre. observed in disproportionation of the chloride anion. Although
Hydrogenation of CO2. These PNP pincer-type iridium the effect of the chloride anion and amines requires further
catalysts (A-H3­C-Cl3) were used in the hydrogenation of investigation, the stabilization of cationic intermediate C-d
carbon dioxide in aqueous triethanolamine solution; the high- would lower the TS for the hydrogen splitting (C-d to C-e) in
est TON, 160000, was achieved with C-HCl2. Representative energy and eventually, the overall energy requirement (¦G ‡)
results are summarized in Figure 4. The homogeneity of this for this catalysis.57 Further investigation of the counter anion
catalytic system was confirmed by a mercury poisoning test showed that use of iodide or acetate resulted in a small drop in
using A-H3 as the catalyst (see the Supporting Informa- the TON for this catalytic system (see Supporting Information).
tion). When the three trihydrido complexes A-H3, [B-H3 + The TON of 160000 recorded by C-HCl2 is the second highest
B-H2amido (77:23)], and C-H3 were compared, A-H3 gave activity ever reported in hydrogenation of carbon dioxide using
the highest TON after 13 h (green bars). The chloride anion amines as a base. The highest reported TON was by a PNP­
lowered the catalytic activities of the pyridine-based PNP com- Ru complex, Ru-tBuPNP (TON ca. 200000),30 with DBU as a
plexes (compare A-H3 with A-H2Cl and A-HCl2), and the base. However, Ru-tBuPNP and the iPr congener Ru-iPrPNP
TONs for B-H2Cl and C-H2Cl were higher than those for the showed significantly lower activities under the aqueous con-
corresponding trihydrido complexes [B-H3 + B-H2amido] and ditions we employed here (TON 4000 for Ru-tBuPNP and 9000
C-H3. In the case of the methoxy-substituted PNP complexes, for Ru-iPrPNP). The introduction of one chloride into B-H3,
the TON was further improved when another chloride was C-H3, and C-H2Cl increased the TONs, but further substitution
introduced in place of hydride (C-HCl2, TON = 160000). A of hydride with chloride anions resulted in considerable
comparison of A-HCl2, B-HCl2, and C-HCl2 shows that the decreases in the activities (B-HCl2 and C-Cl3). The TON of
electron-donating ability of the methoxy group enhanced the C-HCl2 (38000) was higher than those of A-HCl2 and B-HCl2

Bull. Chem. Soc. Jpn. 2016, 89, 113–124 | doi:10.1246/bcsj.20150311 © 2016 The Chemical Society of Japan | 117
 H Cl
i
Pr 2P Ir PiPr2
H
N
recrystallization with recrystallization with
THF/pentane THF/pentane mother liquid
(iii)
OMe
C-H2Cl crystal
crude product (ii)
(i)

Figure 3. Structural changes in C-H2Cl during recrystallization, monitored by 1H NMR (hydride region, left) and 31
P NMR (right)
spectroscopies.

(12000 and 8100, respectively) even in the first hour, suggest- study, C-HCl2 gave the highest TON with an aqueous amine as
ing that the activity (TOF) itself, not only the robustness, was a base.
improved by the introduction of a methoxy group. The catalyst
activity shows good correlation with the observed and calcu- Experimental
lated physical properties listed in the Table 1, namely, the General Procedures. All manipulations involving the air-
chemical shift of hydride in 1H NMR, Ir­H vibration in IR, and and moisture-sensitive compounds were carried out in an
natural atomic charges of Ir and hydride, exhibiting the possi- argon-filled glove box or using standard Schlenk technique
bility to design more active catalysts. However, no significant under argon purified by passing through a hot column packed
increase was observed for a prolonged reaction time, i.e., 40 h with BASF catalyst R3-11. All the solvents used for reactions
(Figure 4, red and blue bars) while it did not reach the were distilled under argon after drying over an appropriate
equilibrium (see the Supporting Information), indicating that drying agent or passed through solvent purification columns.
deactivation is a potential problem for C-HCl2. Most reagents were used without further purification unless
otherwise specified. NMR spectra were recorded on 500 MHz
Conclusion or 400 MHz spectrometers (JEOL JNM-ECP500, JEOL JNM-
In summary, we developed pyrazine-based PNP com- ECS400 and Bruker AscendTM 500). Chemical shifts are
plexes B and p-methoxy-substituted PNP complexes C, which reported in ppm relative to the residual protiated solvent for
catalyse the hydrogenation of carbon dioxide in the presence of 1
H, deuterated solvent for 13C, and external 85% H3PO4 for
triethanolamine. These complexes showed distinct behaviours, 31
P nuclei. Data are presented in the following space: chemical
namely facile hydrogen release (B-H3) and disproportionation shift, multiplicity (s = singlet, d = doublet, t = triplet, vt =
of anionic ligands (C-HCl2). These complexes were used in virtual triplet, q = quartet, m = multiplet, br = broad), cou-
catalytic CO2 hydrogenation. The TON recorded by A-H3 was pling constant in hertz (Hz), and signal area integration in
higher than those by A-H2Cl and A-HCl2. The activities of B- natural numbers. IR spectra were recorded on Shimadzu FTIR-
H3 and C-H3 were promoted by replacement of hydride ligands 8400. [IrCl(coe)2]2,58 py-PNP (1),59 (py-PNP)IrH3 (A-H3),12
with chloride ligands. Among the complexes examined in this (py-PNP)IrH2Cl (A-H2Cl),12 2,6-bis(chloromethyl)pyrazine

118 | Bull. Chem. Soc. Jpn. 2016, 89, 113–124 | doi:10.1246/bcsj.20150311 © 2016 The Chemical Society of Japan
 1.0 M N OH
CO 2 + H 2 3 aq. (5.0 mL) HCOO
(2.5 MPa) (2.5 MPa) cat. (0.010 mmol), THF (0.1 mL), /HBase
150 °C, time

a) Yield of ammonium formate was calculated based on 1H NMR spectrum in D2O with sodium
3-(trimethylsilyl)-1-propanesulfonate as an internal standard. Error bar shows standard errors.
HH H Cl Cl Cl HH H
i
Pr2P Ir PiPr2 i
Pr2P Ir PiPr2 iPr2P Ir PiPr2 iPr2P Ir PiPr2 i
Pr2P Ir PiPr2
H N H N H N HN HN

N N
A-H3 A-H2Cl A-HCl2 B-H3 B-H2amido
H Cl Cl Cl HH H Cl Cl Cl
i
Pr2P Ir PiPr2 i
Pr2P Ir PiPr2 i
Pr2P Ir PiPr2 i
Pr2P Ir PiPr2 iPr2P Ir PiPr2
H N H N H N H N H N

N N
OMe OMe OMe
B-H2Cl B-HCl2 C-H3 C-H2Cl C-HCl2
CO CO
Cl Cl Cl Cl
i
Pr2P Ir PiPr2 i
Pr2P Ru PiPr2 t
Bu2P Ru PtBu2
Cl N H N H N

OMe Ru-iPrPNP Ru-tBuPNP

C-Cl3

Figure 4. Hydrogenation of carbon dioxide catalyzed by Ir(III) pincer complexes using triethanolamine as base.

(3),60 iPr2PH­BH3,61 (tBu)PNP­RuHCl(CO),62 and (iPr)PNP­ in vacuo. The residue was washed with THF (5 mL) and
RuHCl(CO)63,64 were synthesized according to the literature. recrystallized from CHCl3/benzene to give colourless crystal
Standard Procedure for Hydrogenation of Carbon of A-HCl2 (24 mg, 42 ¯mol, 32%). Single crystals suitable for
Dioxide. Catalyst (20 ¯mol) was dissolved in THF (4.0 mL) X-ray crystallography were obtained by recrystallization from
and diluted to 0.10 ¯mol mL¹1. To a 50 mL stainless autoclave, CHCl3/hexane at ¹35 °C. 1H NMR (CDCl3, 400 MHz): ¤ 7.45
the solution of catalyst (100 ¯L, 10 nmol) and degassed aque- (t, 3JHH = 8 Hz, 1H, pyr-H4), 7.16 (d, 3JHH = 8 Hz, 2H, pyr-
ous triethanolamine (1.00 M, 5.00 mL) were charged and H3,H5), 3.78 (d vt, 2JHH = 17 Hz, apparent J = 4 Hz, 2H, P­
pressurized by CO2 (2.5 MPa) and H2 (2.5 MPa). The reaction CH2­pyr), 3.32 (d vt, 2JHH = 17 Hz, apparent J = 4 Hz, 2H, P­
mixture was stirred at 150 °C for 13 h. The yield of ammonium CH2­pyr), 3.16 (m, 2H, P­CH(CH3)2), 2.40 (m, 2H, P­
formate was calculated by 1H NMR in D2O with sodium 3- CH(CH3)2), 1.50 (d vt, 3JHH = 8 Hz, apparent J = 8 Hz, 6H,
(trimethylsilyl)-1-propanesulfonate as an internal standard. CH(CH3)2), 1.42 (d vt, 3JHH = 7 Hz, apparent J = 7 Hz, 6H,
Preparation of (PNP)IrH(Cl)2 (A-HCl2). A solution of A- CH(CH3)2), 1.37 (d vt, 3JHH = 8 Hz, apparent J = 8 Hz, 6H,
H2Cl (74 mg, 130 ¯mol) in CHCl3 (5 mL) was stirred at 70 °C CH(CH3)2), 1.03 (d vt, 3JHH = 7 Hz, apparent J = 7 Hz, 6H,
for 20 h. After the reaction time, the solvent was removed CH(CH3)2), ¹21.81 (t, 2JPH = 12 Hz, 1H, Ir­H); 13C NMR

Bull. Chem. Soc. Jpn. 2016, 89, 113–124 | doi:10.1246/bcsj.20150311 © 2016 The Chemical Society of Japan | 119
 Cl Cl
i
Pr2P Ir Pi Pr 2
H N CO 2
Cl

Cl Cl Cl
i
Pr2 P Ir Pi Pr 2 O i
Pr2P Ir Pi Pr2
H N HCOO N
C-HCl 2

O O
C-f C-a
HCOO

Cl
H O Cl
iPr PiPr 2
2P Ir
O N

H Cl Cl
i O
Pr2P Ir PiPr2 i
Pr2P Ir Pi Pr2
HCOO N C-c HCOO N

O O
C-e H H C-b
Cl
i
Pr2P Ir Pi Pr 2 H2
HBase HCOO N

Base
O
C-d

Scheme 5. Possible catalytic cycle for CO2 hydrogenation catalyzed by C-HCl2.

(CDCl3, 126 MHz): ¤ 165.6 (vt, apparent J = 4 Hz, pyr-C2,C6), To a solution of iPr2PH­BH3 (3.46 g, 26.2 mmol) in THF
135.9 (s, pyr-C4), 120.3 (vt, apparent J = 5 Hz, pyr-C3,C5), (40 mL), nBuLi (1.64 M in hexane, 16.8 mL, 27.6 mmol) was
39.9 (vt, apparent J = 12 Hz, P­CH2­pyr), 25.2 (vt, apparent added dropwise at ¹78 °C and the mixture was stirred at room
J = 13 Hz, P­CH(CH3)2), 22.8 (vt, apparent J = 15 Hz, P­ temperature for 13 h. A solution of the chlorinated pyrazine
CH(CH3)2), 19.9 (m, CH(CH3)), 18.7 (s, CH(CH3)), 18.3 (s, product 3 (2.07 g, total 11.6 mmol) in THF (18 mL) was added
CH(CH3)), 18.2 (s, CH(CH3)); 31P{1H} NMR (CDCl3, 162 to the reaction mixture at ¹78 °C and stirred at room tem-
MHz): ¤ 29.42; IR (powder, cm¹1): ¯Ir­H 2204. HRMS(ESI) perature for 12 h. After the reaction time, the reaction was
[M ¹ Cl]+ Calcd for C19H36ClIrNP2: 568.1641. Found: quenched by adding water (0.5 mL) and the solvent was
568.1629. evaporated in vacuo. Water (30 mL) was added to the mixture
Preparation of pyz-PNP­BH3 (4). pyz-PNP­BH3 (4) was and the product was extracted with CH2Cl2 (40 mL, three
synthesized from 2,6-bis(chloromethyl)pyrazine (3) and iPr2- times). After removal of the solvent in vacuo, reprecipitation of
PLi­BH3 according to a similar procedure in literature.59,65 the residue from hot methanol gave a pale yellow solid 4
2,6-bis(chloromethyl)pyrazine (3) was synthesized from (2.20 g, 5.98 mmol, 20% yield from 2,6-dimethylpyrazine).
2,6-dimethylpyrazine (2) (3.24 g, 30 mmol) according to the 1
H NMR (500 MHz, CDCl3): ¤ 8.45 (s, 2H, pyz-H3,H5),
literature.61 Purification with silica-gel column chromatography 3.19 (d, 2JPH = 11 Hz, 4H, P­CH2­pyz), 2.17­2.09 (m, 4H, P­
(dichloromethane, hexane = 3:1, Rf = 0.21) gave brown oil CH(CH3)2), 1.20 (ddd, J = 16, 9, 6 Hz, 24H, CH(CH3)2),
(2.07 g, gradually decomposed under air), which contaminated ¹0.08 to 0.73 (br m, 6H, BH3); 13C NMR (101 MHz, CDCl3):
2-(dichloromethyl)-6-methylpyrazine and the crude product ¤ 150.2 (2JPC = 6 Hz, pyz-C2,C6), 143.7 (d, 3JPC = 2 Hz, pyz-
was used in the next step without further purification. C3,C5), 27.8 (d, 1JPC = 25 Hz, P­CH2­pyz), 22.1 (d, 1JPC =

120 | Bull. Chem. Soc. Jpn. 2016, 89, 113–124 | doi:10.1246/bcsj.20150311 © 2016 The Chemical Society of Japan
31 Hz, P­CH(CH3)2), 17.2 (d, 2JPC = 11 Hz, CH(CH3)2); To a solution of B-H2Cl (13 mg, 198 mmol) in THF (4 mL),
31
P{1H} NMR (202 MHz, CDCl3): ¤ 38.95­37.63 (m); finely ground CsOH­H2O (100 mg, 596 mmol) was added and
11
B{1H} NMR (160 MHz, CDCl3): ¤ ¹43.7 to ¹45.3 (m); the resulting mixture was stirred at room temperature for one
Anal. Calcd for C18H40B2N2P2: C, 58.73; H, 10.95; N, day. During that time, the suspension turned to dark red
7.61%. Found: C, 58.55; H, 10.98; N, 7.36%; HRMS(ESI) solution. After completion of the reaction was confirmed by
[M ¹ 2BH3 + Na]+ Calcd for C18H34N2NaP2: 363.2095. 31
P NMR, the solvent was removed under reduced pressure.
Found: 363.2097; mp 143.0­146.5 °C (decomp.). The product was extracted with toluene and recrystallized from
Preparation of pyz-PNP Ligand (5). Ligand 5 was synthe- benzene/heptane to give red solid B-H2amido (65 mg, 121
sized from pyz-PNP­BH3 (4) according to a similar procedure ¯mol, 62%). The signals of NMR spectra were broadened
in literature.66 A suspension of pyz-PNP­BH3 (4) (478 mg, 1.30 and it implied an equilibrium between multiple species. The
mmol) in degassed morpholine (10 mL) was heated at 90 °C full assignment of the each signal was unsuccessful because
for 15 h. The reaction progress was monitored by 31P and of the broadness, and 31P NMR is shown in the Supporting
11
B NMR. The reaction mixture was cooled to room temperature Information.
and concentrated under reduced pressure. The product was Preparation of Mixture of (pyz-PNP*)Ir(H)2 (B-H2amido)
extracted with toluene (5 mL, 2 mL © 3). The combined organic and (pyz-PNP)IrH3 (B-H3). This reaction is performed
phase was washed with degassed water (2 mL). Concentration according to a similar procedure in literature.12
of the organic phase gave brown oil (360 mg, 81%), which was To a solution of B-H2Cl (113 mg, 0.20 mol) in THF (4 mL),
used in the next step without further purification. NaH (100 mg, 4.2 mmol) was added and the resulting mixture
1
H NMR (400 MHz C6D6): ¤ 8.43 (s, 2H, pyz-H5), 2.75 (d, was stirred at room temperature for one day. During that time,
2
JPH = 1 Hz, 4H, P­CH2­pyz), 1.62 (m, 4H, P­CH(CH3)2), the suspension turned to dark red solution. After confirma-
1.01­0.95 (m, 24H, CH(CH3)2); 13C NMR (101 MHz, CDCl3): tion of the reaction completion by 31P NMR, the solvent was
¤ 155.9 (d, 2JPC = 9 Hz, pyz-C2,C6), 142.2 (d, 3JPC = 7 Hz, removed in vacuo. The residue was extracted with toluene and
pyz-C3,C5), 29.9 (d, 1JPC = 26 Hz, P­CH2­pyz), 23.9 (d, recrystallized from cold hexane to give red crystal (65 mg,
1
JPC = 16 Hz, P­CH(CH3)2), 19.9 (d, 2JPC = 15 Hz, CH(CH3)2), 121 ¯mol, 62%), mixture of B-H3 and B-H2amido. The ratio
19.2 (d, 2JPC = 12 Hz, CH(CH3)2); 31P{1H} NMR (162 MHz, of the B-H3 and B-H2amido was different in each experiment.
C6D6): ¤ 12.80 (s); HRMS(ESI) [M + H]+ Calcd for The ratio of B-H3 increased by treating the reaction mixture (23
C18H35N2P2: 341.2275. Found: 341.2266. mg) in THF-d8 (1.5 mL) with H2 (5.0 MPa) at room temperature
Preparation of (pyz-PNP)IrH2Cl (B-H2Cl). B-H2Cl was for 17 h. Data of B-H3 is shown below. 1H NMR (THF-d8,
synthesizd from pyz-PNP (5) according to a similar procedure 500 MHz): ¤ 8.16 (s, 2H, pyz-H3,H5), 3.30 (vt, apparent J =
in literature.12 To a 50 mL stainless autoclave, [IrCl(coe)2]2 4 Hz, P­CH2­pyz, 4H), 1.91 (m, P­CH(CH3)2, 4H), 1.14 (d vt,
(342 mg, 0.38 mmol), pyz-PNP ligand (5, 368 mg, 1.08 mmol), 3
JHH = 8 Hz, apparent J = 8 Hz, 12H), 1.07 (d vt, 3JHH = 7 Hz,
and THF (15 mL) were charged under argon atmosphere. The apparent J = 7 Hz, 12H), ¹10.70 (td, 2JHH = 5 Hz, 2JPH =
mixture was pressurized by hydrogen (2.5 MPa) and stirred at 17 Hz, 2H), ¹19.83 (tt, 2JHH = 5 Hz, 2JPH = 14 Hz, 1H);
80 °C for seven hours. The solvent was removed in vacuo and 13
C NMR (THF-d8, 101 MHz): ¤ 158.3 (vt, apparent J = 5 Hz,
the residue was reprecipitated from THF/hexane. After wash- pyz-C2,C6), 139.5 (vt, apparent J = 5 Hz, pyz-C3,C5), 40.9 (vt,
ing the residue with hexane, colourless solid was obtained. B- apparent J = 12 Hz, P­CH2­pyz), 27.6 (vt, apparent J = 15
H2Cl (354 mg, 750 ¯mol, 80%). Single crystals suitable for Hz, P­CH(CH3)2), 19.7 (m, CH(CH3)2), 18.8 (s, CH(CH3));
X-ray crystallography were obtained by recrystallization from P{ H} NMR (THF-d8, 202 MHz): ¤ 57.9; IR (KBr, cm¹1):
31 1

THF/pentane at ¹35 °C. 1H NMR (C6D6, 400 MHz): ¤ 8.04 (s, ¯Ir­H 2094, 1717. HRMS(ESI) [B-H3 + MeCN ¹ H]+ Calcd for
2H, pyz-H3,H5), 3.18 (d vt, 2JHH = 17 Hz, apparent J = 4 Hz, C20H39IrN3P2: 576.2248. Found: 576.2273.
2H, P­CH2­pyz), 2.88 (m, 2H, P­CH(CH3)2), 2.59 (d vt, Preparation of (yz-PNP)IrH(Cl)2 (B-HCl2). A solution
2
JHH = 17 Hz, apparent J = 4 Hz, 2H, P­CH2­pyz), 1.59 (m, of B-H2Cl (79 mg, 140 ¯mol) in CHCl3 (5 mL) was stirred at
2H, P­CH(CH3)2), 1.49 (d vt, 3JHH = 8 Hz, apparent J = 8 Hz, 70 °C for one day. After the reaction, the solvent was removed
6H, CH(CH3)2), 1.12 (d vt, 3JHH = 7 Hz, apparent J = 7 Hz, in vacuo. The residue was reprecipitated from THF/pentane
6H, CH(CH3)2), 1.03 (d vt, 3JHH = 8 Hz, apparent J = 8 Hz, and recrystallized from THF/pentane to give light brown crys-
6H, CH(CH3)2), 0.68 (d vt, 3JHH = 7 Hz, apparent J = 7 Hz, tals of B-HCl2 (18 mg, 32 ¯mol, 23%). Single crystals suitable
6H, CH(CH3)2), ¹17.77 (td, 2JHH = 8 Hz, 2JPH = 13 Hz, 1H, for X-ray crystallography were obtained by recrystallization
Ir­H), ¹21.37 (td, 2JHH = 8 Hz, 2JPH = 15 Hz, 1H, Ir­H); from toluene/hexane at ¹35 °C.
13
C NMR (C6D6, 101 MHz): ¤ 157.8 (vt, apparent J = 5 Hz, 1
H NMR (CDCl3, 500 MHz): ¤ 8.35 (s, 2H, pyz-H3,H5),
pyz-C2,C6), 140.5 (vt, apparent J = 5 Hz, pyz-C3,C5), 40.0 3.67 (d vt, 2JHH = 17 Hz, apparent J = 4 Hz, 2H, P­CH2­pyz),
(vt, apparent J = 12 Hz, P­CH2­pyz), 24.9 (m, P­CH(CH3)2), 3.24 (d vt, 2JHH = 17 Hz, apparent J = 4 Hz, 2H, P­CH2­pyz),
21.1 (br s, CH(CH3)), 20.6 (vt, apparent J = 3 Hz, CH(CH3)), 3.19 (m, 2H, P­CH(CH3)2), 2.42 (m, 2H, P­CH(CH3)2), 1.51 (d
19.0 (s, CH(CH3)), 17.2 (s, CH(CH3)); 31P NMR (C6D6, 162 vt, 3JHH = 8 Hz, apparent J = 8 Hz, 6H, CH(CH3)2), 1.43 (d vt,
MHz): ¤ 48.9; IR (KBr, cm¹1): ¯Ir­H 2176, 2098. HRMS(EI) 3
JHH = 7 Hz, apparent J = 7 Hz, 6H, CH(CH3)2), 1.37 (d vt,
[M + MeCN ¹ Cl]+ Calcd for C20H39IrN3P2: 576.2248. 3
JHH = 8 Hz, apparent J = 8 Hz, 6H, CH(CH3)2), 1.05 (d vt,
Found: 576.224. 3
JHH = 8 Hz, apparent J = 8 Hz, 6H), ¹20.44 (t, 2JPH = 12 Hz,
Preparation of (pyz-PNP*)Ir(H)2 (B-H2amido). B- 1H, Ir­H); 13C NMR (CDCl3, 126 MHz): ¤ 160.5 (vt, apparent
H2amido was synthesize from B-H2Cl according to a similar J = 4 Hz, pyz-C2,C6), 141.0 (vt, apparent J = 5 Hz, pyz-
procedure in literature.12 C3,C5), 36.6 (vt, apparent J = 11 Hz, P­CH2­pyz), 25.4 (vt,

Bull. Chem. Soc. Jpn. 2016, 89, 113–124 | doi:10.1246/bcsj.20150311 © 2016 The Chemical Society of Japan | 121
apparent J = 14 Hz, P­CH(CH3)2), 23.1 (vt, apparent J = 15 1
H NMR (THF-d8, 500 MHz): ¤ 6.87 (s, 2H, pyr-H3,H5),
Hz, P­CH(CH3)2), 19.8 (s, CH(CH3)), 18.6 (s, CH(CH3)), 18.3 3.80 (s, 3H, OCH3), 3.75 (d vt, 2JHH = 16 Hz, apparent J =
(s, CH(CH3)), 18.1 (s, CH(CH3)); 31P{1H} NMR (CDCl3, 162 4 Hz, 2H, P­CH2­pyr), 3.48 (d vt, 2JHH = 17 Hz, apparent J =
MHz): ¤ 30.82; IR (powder, cm¹1): ¯Ir­H 2214. HRMS(ESI) 4 Hz, 2H, P­CH2­pyr), 2.77 (m, 2H, P­CH(CH3)2), 1.98 (m,
[M ¹ HCl2]+ Calcd for C18H34IN2P2: 533.1826. Found: 2H, P­CH(CH3)2), 1.34 (d vt, 3JHH = 8 Hz, apparent J = 8 Hz,
533.1805. 6H, CH(CH3)2), 1.30 (d vt, 3JHH = 7 Hz, apparent J = 7 Hz,
Preparation of 4-Methoxy-2,6-dimethylpyridine (7). 4- 6H, CH(CH3)2), 1.09 (d vt, 3JHH = 8 Hz, apparent J = 8 Hz,
Methoxy-2,6-dimethylpyridine (7) was synthesizd from 4- 6H, CH(CH3)2), 0.88 (d vt, 3JHH = 7 Hz, apparent J = 7 Hz,
hydroxy-2,6-dimethylpyridine (6) (3.24 g, 30 mmol) according 6H, CH(CH3)2), ¹19.83 (td, 2JHH = 8 Hz, 2JPH = 13 Hz, 1H,
to a similar procedure in literature.67 Ir­H), ¹23.01 (td, 2JHH = 8 Hz, 2JPH = 15 Hz, 1H, Ir­H);
A suspension of 6 (1.85 g, 15.0 mmol), dimethyl sulfate 13
C NMR (C6D6, 126 MHz): ¤ 164.9 (s, pyr-C4), 164.4 (vt,
(1.47 mL, 15.5 mmol) and potassium carbonate (6.09 g, 44.1 apparent J = 4 Hz, pyr-C2,C6), 105.4 (vt, apparent J = 5 Hz,
mmol) in anhydrous acetone (56 mL) was heated under reflux pyr-C3,C5), 54.9 (s, OCH3), 43.9 (vt, apparent J = 12 Hz,
for 2 h. After cooling to 0 °C the mixture was filtered through a P­CH2­pyr), 24.8 (m, P­CH(CH3)2), 21.2 (vt, apparent J =
short plug of silica on a glass filter. The filtrate was concen- 3 Hz, CH(CH3)), 20.8 (vt, apparent J = 3 Hz, CH(CH3)), 19.3
trated to provide 7 (1.53 g, 11.1 mmol, yield) as yellow spec- (s, CH(CH3)), 17.4 (s, CH(CH3)); 31P{1H} NMR (C6D6, 202
trooscopic data were consistent with the literature.68 MHz): ¤ 48.7; IR (KBr, cm¹1): ¯Ir­H 2176, 2098. HRMS(ESI)
Preparation of pOMe-PNP Ligand 8. 4-Methoxy-PNP [M ¹ Cl]+ Calcd for C20H39IrNOP2: 564.2136. Found:
was synthesized from 4-methoxy-2,6-dimethylpyridine (7) 564.2134.
according to a similar procedure in literature.69,70 Preparation of ( pOMe-PNP)Ir(H)3 (C-H3). C-H3 was
To a solution of 2,6-dimethyl-4-methoxypyridine 7 (686 synthesized from C-H2Cl according to a similar procedure in
mg, 5.00 mmol) and N,N,N¤,N¤-tetramethylethylenediamine literature.12
(1.6 mL, 11 mmol) in Et2O (13 mL), nBuLi (2.66 M in hexane, To a solution of C-H2Cl (+C-HCl2) (100 mg, 0.17 mmol)
4.0 mL, 10.6 mmol) was added dropwise at 0 °C and the mix- in THF (10 mL), NaH (50 mg, 2 mmol) was added and the
ture was allowed to warm to room temperature with stirring for resulting mixture was stirred at room temperature for 1 day.
5 h. A solution of iPr2PCl (1.70 g, 11.2 mmol) in Et2O (10 mL) During that time, the suspension turned to a dark red solution.
was added to the resulting mixture dropwise at ¹78 °C and After confirmation of the completion by 31P NMR, the solvent
stirred at room temperature for 21 h. After the reaction, the was removed in vacuo. The residue was extracted with hexane
resulted solid was removed by filtration through a pad of Celite, and recrystallized from cold hexane to afford off-white solid
and the filtrate was concentrated by evaporation. The obtained (C-H3, 21 mg, 37 ¯mol, 22%).
crude product was purified by passing through a short plug of 1
H NMR (C6D6, 500 MHz): ¤ 6.25 (s, 2H, pyr-H3,H5), 3.12
silica gel on a glass filter with Et2O as an eluent. The solvent (s, 3H, OCH3), 3.01 (vt, apparent J = 3 Hz, 2H, P­CH2­pyr),
was removed to give light brown oil of 8 (1.64 g), which was 1.85 (m, 2H, P­CH(CH3)2), 1.28 (d vt, 3JHH = 8 Hz, apparent
used in the next step without further purification. 1H NMR J = 8 Hz, 12H, CH(CH3)2), 1.18 (d vt, 3JHH = 7 Hz, apparent
(400 MHz, C6D6): ¤ 6.78 (s, 2H, pyr-H3,H5), 3.20 (s, 3H, J = 7 Hz, 12H, CH(CH3)2), ¹10.47 (td, 2JPH = 17 Hz, 2JHH =
O­CH3), 2.98 (d, 2JPH = 1 Hz, 4H, P­CH2­pyr), 1.79­1.67 (m, 5 Hz, 2H, Ir­H), ¹20.53 (tt, 2JPH = 14 Hz, 2JHH = 5 Hz, 1H,
4H, P­CH(CH3)2), 1.11­1.03 (m, 24H, CH(CH3)2); 13C NMR Ir­H); 13C NMR (C6D6, 126 MHz): ¤ 163.9 (vt, apparent J = 4
(101 MHz, CDCl3): ¤ 166.5 (s, C­O­CH3), 162.0 (d, 2JPC = Hz, pyr-C2,C6), 163.5 (s, pyr-C4), 104.6 (vt, apparent J = 5
10 Hz, pyr-C2,C6), 106.8 (d, 3JPC = 7 Hz, pyr-C3,C5), 54.3 (s, Hz, pyr-C3,C5), 54.7 (s, OCH3), 45.1 (vt, apparent J = 12
O­CH3), 33.2 (d, 1JPC = 23 Hz, P­CH2­pyr), 23.9 (d, 1JPC = Hz, P­CH2­pyr), 27.1 (vt, apparent J = 15 Hz, P­CH(CH3)2),
16 Hz, P­CH(CH3)2), 19.9 (d, 2JPC = 14 Hz, CH(CH3)2), 19.3 20.0 (vt, apparent J = 3 Hz, CH(CH3)2), 19.1 (s, CH(CH3)2);
(d, 2JPC = 11 Hz, CH(CH3)2); 31P{1H} NMR (162 MHz, C6D6): P{ H} NMR (C6D6, 162 MHz): ¤ 57.8; IR (KBr, cm¹1):
31 1

¤ 11.64; HRMS(ESI) [M + H]+ Calcd for C20H38NOP2: ¯Ir­H 2083, 1686. HRMS(ESI) [M ¹ H]+ Calcd for C20H39-
370.2429. Found: 370.2417. IrNOP2: 564.2136. Found: 564.2111.
Preparation of ( pOMe-PNP)IrH2Cl (C-H2Cl). C-H2Cl Preparation of ( pOMe-PNP)IrH(Cl)2 (C-HCl2). A
was synthesized from p-OMe-PNP (5) according to a similar solution of C-H2Cl (+C-HCl2) (50 mg, 85 ¯mol) in CHCl3
procedure in literature.12 (5 mL) was stirred at room temperature for 20 h. After the
To a 50 mL stainless autoclave, [IrCl(coe)2]2 (448 mg, 0.500 completion of the reaction confirmed by 31P NMR, the solvent
mmol), pOMe-PNP (8, 406 mg, 1.10 mmol), and THF (20 mL) was removed in vacuo. The product was recrystallized from
were charged under argon atmosphere. The mixture was pres- CHCl3/pentane to give colourless crystal of C-HCl2 (17 mg,
surized by hydrogen (3.0 MPa) and stirred at 80 °C for 12 h. 27 ¯mol, 32%). Single crystals suitable for X-ray crystallog-
The solvent was removed in vacuo and the residue was raphy were obtained by recrystallization from CHCl3/pentane.
reprecipitated from THF/hexane. The residue was washed with 1
H NMR (CDCl3, 500 MHz): ¤ 6.72 (s, 2H, pyr-H3,H5),
hexane to give a pale-yellow solid. Because of the facile 3.81 (s, 3H, OCH3), 3.72 (d vt, 2JHH = 16 Hz, apparent J =
disproportionation in the reaction condition and high crys- 2 Hz, 2H, P­CH2­pyr), 3.27 (d vt, 2JHH = 17 Hz, apparent J =
tallinity of C-HCl2, a mixture of C-H2Cl and C-HCl2 (414 mg) 2 Hz, 2H, P­CH2­pyr), 3.14 (m, 2H, P­CH(CH3)2), 2.38 (m,
was obtained (C-H2Cl/C-HCl2 = 1/0.16). Subsequent recrys- 2H, P­CH(CH3)2), 1.49 (d vt, 3JHH = 8 Hz, apparent J = 8 Hz,
tallizations from THF/pentane twice and extraction with THF 6H, CH(CH3)2), 1.40 (d vt, 3JHH = 7 Hz, apparent J = 7 Hz,
gave a mixture of C-H2Cl and C-HCl2 at the ratio of 1/0.07. 6H, CH(CH3)2), 1.35 (d vt, 3JHH = 8 Hz, apparent J = 8 Hz,

122 | Bull. Chem. Soc. Jpn. 2016, 89, 113–124 | doi:10.1246/bcsj.20150311 © 2016 The Chemical Society of Japan
6H, CH(CH3)2), 1.03 (d vt, 3JHH = 7 Hz, apparent J = 7 Hz, and 1402673 for complex C-HCl2. Copies of the data can be
6H, CH(CH3)2), ¹22.50 (t, 2JPH = 12 Hz, 1H, Ir­H); 13C NMR obtained free of charge via http://www.ccdc.cam.ac.uk/conts/
(CDCl3, 126 MHz): ¤ 166.1 (vt, apparent J = 4 Hz, pyr-C2,C6), retrieving.html (or from the Cambridge Crystallographic Data
165.4 (s, pyr-C4), 106.5 (vt, apparent J = 5 Hz, pyr-C3,C5), Centre, 12, Union Road, Cambridge, CB2 1EZ, UK; Fax: +44
56.0 (s, OCH3), 40.2 (vt, apparent J = 12 Hz, P­CH2­ 1223 336033; e-mail: [email protected]).
pyr), 25.2 (vt, apparent J = 14 Hz, P­CH(CH3)2), 22.8 (vt,
apparent J = 15 Hz, P­CH(CH3)2), 19.9 (m, CH(CH3)2), 18.7 A part of this work was conducted in Research Hub for
(s, CH(CH3)2), 18.2 (s, CH(CH3)2), 18.1 (s, CH(CH3)2); Advanced Nano Characterization, The University of Tokyo,
P{ H} NMR (CDCl3, 202 MHz): ¤ 28.81; IR (powder,
31 1
supported by MEXT, Japan. The computations were performed
cm¹1): ¯Ir­H 2214. HRMS(ESI) [M ¹ Cl]+ Calcd for C20H38- using Research Centre for Computational Science, Okazaki,
ClIrNOP2: 598.1746. Found: 598.1750. Japan.
Preparation of ( pOMe-PNP)Ir (Cl)3 (C-Cl3). To a solu-
tion of hexachloroethane (52 mg, 0.22 mmol) in THF (1 mL) in Supporting Information
a 20-mL Schlenk tube was added a solution of [IrCl(coe)2]2 Experimental procedure, additional experimental results,
(89 mg, 0.1 mmol) and pOMe-PNP ligand (8, 74 mg, 0.2 mmol) detail for the X-ray structural analysis, and the detail for the
in THF (2 mL). After stirring for 1 day at 65 °C, the mix- theoretical calculations. This material is available on http://
ture was dried in vacuo. After the repetitive and exhaustive dx.doi.org/10.1246/bcsj.20150311.
purification, (reprecipitation from CH2Cl2/hexane, extraction
with benzene, reprecipitation from CHCl3/benzene and then
from CH2ClCH2Cl/benzene) a pale yellow powder of C-Cl3 References
was obtained (10 mg, 0.015 mmol, 7.5%). 1 Ullmann’s Encyclopedia of Industrial Chemistry, WILEY-
1
H NMR (CDCl3, 500 MHz): ¤ 6.84 (s, 2H, pyr-H3,H5), VCH, 2009, and references therein. doi:10.1002/14356007.
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