Angewandte
Communications
Chemie
filtrated and the solvent was removed under reduced pressure. Water
4.0 mL) was added to the brown residue and the insoluble material
Acknowledgements
(
was removed by filtration. The solvent was removed under reduced
This work was supported by Grants-in-Aid: 26000008 (Spe-
cially Promoted Research), 16K05727, and 15K05566 from
the Ministry of Education, Culture, Sports, Science and
Technology (MEXT), Japan and the World Premier Interna-
tional Research Center Initiative (WPI), Japan.
pressure to generate a brown powder of 1, which was dried in vacuo
III
5
(
yield: 74% based on [Ir (h -C Me )Cl ] ). Complex 1 was recrystal-
5 5 2 2
lized by diffusion of diethyl ether into its acetone solution, suitable for
+
X-ray analysis. ESI-MS (in methanol): m/z 641.1 {[1-Cl] , relative
ꢀ1
intensity (I) = 100% in the range m/z 200–2000}. FT-IR (cm , solid
state): 2986 (aliphatic CꢀH), 2960 (aliphatic CꢀH), 2924 (aliphatic Cꢀ
H), 2852 (aliphatic CꢀH), 1459 (aromatic C=C), 1439 (aromatic C=
1
C), 1374 (aromatic C=C). H NMR (300 MHz, in D O, referenced to
2
Conflict of interest
TSP, 258C): d 1.75 {s, 15H, C (CH ) }, 2.17–3.66 (m, 14H, -CH -), 2.70
5
3
5
2
(
5
s, 6H, N-CH ). Anal. Cald for 1 (C H N Cl S NiIr): C, 33.69; H,
3 19 35 2 2 2
The authors declare no conflict of interest.
.21; N, 4.14%. Found: C, 33.64; H, 5.26; N, 4.09%.
II
III
5
II
III
5
[
Ni Cl(X)Ir (m-H)(h -C Me )] (2): [Ni Cl(X)Ir Cl(h -C Me )]
5
5
5
5
Keywords: bioinorganic chemistry · carbon monoxide ·
dehydrogenase · hydrogenase · hydrogen
(1) (50.8 mg, 0.075 mmol) was dissolved in water (8.0 mL) and it was
stirred for 5 h under an H atmosphere (0.8 MPa) at room temper-
2
ature. The solvent of the resulting solution was evaporated, and
acetone (4.0 mL) was added to the residue. The insoluble material
was removed by filtration and the solvent was removed by evapo-
ration to yield a yellow power of 2, which was dried in vacuo (yield:
7
2% based on 1). Complex 2 was recrystallized by diffusion of diethyl
[1] Special issue on “Toward a Hydrogen Economy”, Science 2004,
305, 957 – 976.
ether into its acetone solution under an N atmosphere, suitable for X-
ray analysis. ESI-MS (in methanol): m/z 607.1 ([2-Cl] , I = 100% in
2
+
ꢀ
1
the range m/z 200–2000). FT-IR (cm , KBr disk): 2956 (aliphatic Cꢀ
H), 2917 (aliphatic CꢀH), 2851 (aliphatic CꢀH), 1954 (NiꢀHꢀIr) 1641
[
3] a) Special issue on “Hydrogenases”, Eur. J. Inorg. Chem. 2011,
aromatic C=C), 1470 (aromatic C=C), 1460 (aromatic C=C), 1451
aromatic C=C) 1427 (aromatic C=C). Anal. Cald for 2·CH COCH
C H N OClS NiIr): C, 37.69; H, 6.04; N, 4.00%. Found: C, 37.70;
9
(
(
(
3
3
2
2
42
2
2
H, 5.89; N, 4.27%.
II
III
5
II
III
[
Ni (X)Ir (CO)(h -C Me )](PF ) {[3](PF ) }: [Ni Cl(X)Ir Cl-
5 5 6 2 6 2
5
(h -C Me )] (1) (41.0 mg, 0.060 mmol) was dissolved in water
5 5
(5.0 mL) and it was stirred for 1 h under a CO atmosphere at room
temperature. The resulting solution was filtered and the filtrate was
evaporated to yield a red powder of [3](Cl) (yield: 97% based on 1),
which is used for the reactions in water as a water-soluble complex.
An aqueous solution (2.0 mL) of KPF (71 mg, 0.39 mmol) was added
[
2
[
[
6
to the aqueous solution of [3](Cl) to generate a red solid, which was
2
collected by filtration. Acetone (2.0 mL) was added to the solid and
the insoluble material was removed by filtration. The solvent was
removed under reduced pressure to yield a red powder of [3](PF6)2
[
[
(yield: 43% based on 1). Complex 3 was recrystallized by diffusion of
diethyl ether into its acetone solution under an N2 atmosphere,
suitable for X-ray analysis. ESI-MS (in acetonitrile): m/z 317.1 ([3]
I = 100% in the range m/z 200–2000). FT-IR (cm , KBr disk): 3009
2
+
,
[
ꢀ
1
(
(
aliphatic CꢀH), 2919 (aliphatic CꢀH), 2867 (aliphatic CꢀH), 2037
CꢁO), 1629 (aromatic C=C), 1479 (aromatic C=C), 1464 (aromatic
1
C=C), 1436 (aromatic C=C), 838 (PF ). H NMR (300 MHz, in
6
[
D ]acetone, referenced to TMS, 258C): d 2.20 {s, 15H, C (CH ) },
6 5 3 5
[12] F. A. Cotton, G. Wilkinson, C. A. Murillo, M. Bochmann,
Advanced Inorganic Chemistry, 6th ed., Wiley, New York,
1999, pp. 636 – 639.
2
3
2
.42–3.68 (m, 14H, -CH -), 2.87 (s, 6H, N-CH ). Anal. Cald for
2 3
·(PF ) ·CH COCH (C H N O F P S NiIr): C, 28.12; H, 4.21; N,
6
2
3
3
23 41
2
2
12
2
2
.85%. Found: C, 28.00; H, 4.19; N, 2.92%.
II
III
5
II
III
5
[
Ni (OH)(X)Ir (COOH)(h -C Me )] (4): [Ni Cl(X)Ir Cl(h -
5 5
C Me )] (1) (138 mg, 0.20 mmol) was dissolved in water (8.0 mL)
and it was stirred for 1 h under a CO atmosphere at room temper-
ature. To the resulting solution was added 1.0m NaOH/H O
5
5
2
(0.50 mL) to yield a light-green powder of 4, which was collected by
filtration and dried in vacuo (yield: 87% based on 1). ESI-MS (in
+
acetonitrile): m/z 651.1 ([4-OH] , I = 100% in the range m/z 200–
ꢀ
1
2
000). FT-IR (cm , solid state): 2954 (aliphatic CꢀH), 2907 (aliphatic
CꢀH), 2845 (aliphatic CꢀH), 1610 (C=O), 1464 (aromatic C=C), 1435
(
(
aromatic C=C), 1423 (aromatic C=C). Anal. Cald for
C H O N S NiIr): C, 35.93; H, 5.58; N, 4.19%. Found: C, 36.10;
4
Manuscript received: May 11, 2017
Accepted manuscript online: June 6, 2017
Version of record online: && &&, &&&&
2
0
37
3
2 2
H, 5.48; N, 4.16%.
4
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 5
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