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TRANSCRIPT
No.1
26 172
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/
* Pt Ir *
MeOH * * 12.6 wt%H2
* 3d MeOH*
3dMeOH *
/ 2-Aminophenol(apH2), 2-Aminophenolate(apH–), apH– o- (II) (trans-[FeII(apH)2(MeOH)2] (1))
MeOH apH–
3- -3,4--2- (II)
*
MeOH
* MeOH
ππExcited State Hydrogen
Detachment* MeOH
*
No. I. 1. Nonprecious-metal-assisted Photochemical Hydrogen Evolution from ortho-Phenylenediamine Takeshi Matsumoto, Junki Ishii, Masanori Wakizaka, and Ho-Chol Chang 5th Asian Conference on Coordination Chemistry (ACCC5), OL2, Hong Kong, 2015, 7, 12-16.
2. -o- (II) MeOH
, , ,
27 , O-22A, , 2015, 8, 7-9.
II. 1. Photochemical Hydrogen Evolution Mediated by Iron(II) Complex with ortho-Phenylenediamine Takeshi Matsumoto and Ho-Chol Chang International Chemical Congress of Pacific Basin Societies (Pacifichem2015), ENRG 706, Honolulu, Hawai, 2015, 12, 15-20. 2. Synthesis and Photochemical Properties of New 2-aminophenolato Complexes Ryota Tanaka, Masanori Wakizaka, Takeshi Matsumoto, and Ho-Chol Chang International Chemical Congress of Pacific Basin Societies (Pacifichem2015), INOR 1080, Honolulu, Hawai, 2015, 12, 15-20. 3. Physicochemical Properties of the Oxidized forms of Pt(II)-diimine Complexes with Catecholato and Benzenedithiolato Shota Yamada, Masanori Wakizaka, Takeshi Matsumoto, and Ho-Chol Chang International Chemical Congress of Pacific Basin Societies (Pacifichem2015), INOR 1904, Honolulu, Hawai, 2015, 12, 15-20.
III. 1. Exploring the Inherent Photocatalytic Activity of o-Aminophenol, o-Aminophenolate, and an Its Fe(II) Complex for the Dehydrogenation of MeOH at Room Temperature Masanori Wakizaka, Ryota Tanaka, Takeshi Matsumoto, Akane Usui, Atsushi Kobayashi, Masako Kato, Ho-Chol Chang Submitted. 2. Highly Polar Solvent-induced Disproportionation of Cationic Pt(II)-diimine Complex with o-Semiquinonato Shota Yamada, Takeshi Matsumoto, Masanori Wakizaka, Ho-Chol Chang to be submitted.
No. ( )
*
MeOH (12.6 at%H2)* Olah (Methanol
Economy) * (J. Am. Chem. Soc. 2011, 133, 12881-12898.) MeOH* (200-300 °C) *
Beller Grützmacher Ru ( 90 °C)MeOH *
(Beller, M. et. al., Nature 2013, 495, 85-89. Grützmacher, H. et. al., Nat. Chem. 2013, 5, 342-347. Figure 1)
MeOH
* 2013
o-Phenylenediamine(opda)([FeII(opda)3]2+)
([FeII(opda)l(s-bqdi)m(bqdi)n]2+(l + m + n = 3, s-bqdi = semi-benzoquinodiimine, bqdi = o-benzoquinodiimine)
(J. Am. Chem. Soc. 2013, 135, 8646-8654. Scheme 1) opda 1ππ*
(Conical Intersection)1πσ* opda N–H
2014 Pino 2-Aminophenol(apH2)O–H (J. Phys. Chem. A
2014, 118, 2056-2062.)
* apH2 apH2 2-Aminophenolate(apH–) apH–
Fe(II) ([FeII(apH)2(MeOH)2])(1) MeOH
MeOH * ( )
1 apH2
tetrabutylammonium hydroxide(TBAOH)FeII(ClO4)2·6H2O
(Scheme 2) Figure 21( ) apH2( ) apH–( )
MeOH apH2 apH– 230 nm 285 nmππ* * 1
230, 285, 335, 460 nm 2 apH2 apH–
ππ* * 2 CT * 1 KBr disk MeOH
NNRuII
HK(dme)2
RuIIHN
P
CO
PH
Cl
iPriPr
iPriPr
Beller (2013) Grützmacher (2013)
Figure 1. �P��4MeOH8&5�<�
Scheme 1. [FeII(opda)3]2+A�I2K�&50/ �
H2N
NH2
FeII
3
FeII
NN
NN
N NHH2
H2
HH2
Hm
l
n
H2
hv(λ < 300 nm)
l + m + n = 3
Scheme 2. A�1P��
H2N
OFeII
NH2
OO
O
MeH
Me HOH
NH2 2TBAOHFeII(ClO4)2·6H2O
MeOH
apH2 1
No.
1 MeOH
apH2 MeOH 200 W Hg-Xe289 ± 10 nm
(GC)*
5 apH2 4.1 eq. 24 6.5 eq.
* (Figure 3, ) apH– 1
(Figure 3, ) MeOH
(Table 1)FeII(ClO4)2·6H2O MeOH MeOH
(Figure 3, ) apH*
apH2 apH– 1ππ**
MeOH * HCHOHCO2H (Table 1)
apH2 apH– 1MeOH
1 350 ± 10 nmaoH–
Fe(II) apH–
apH2, apH–, 1 MeOH
MeOH-d3(CD3OH)apH2, apH–, 1
GC Figure 4
5.0 (p-H2), 6.3 (o-H2), 7.8 (p-D2), 8.4 (o-D2),
6.4 min (HD) (Figure 4a-4c) apH2, apH–, 1 MeOH-d3
289 ± 10 nm 24 hGC
6.4 min(Figure 4d-4f)3 MeOH-d3
Figure 2. apH2 (2 mM, F7), apH– (2 mM, 67), A�1 (1.35 mM, >7)PMeOH�GHTQA�1P��.�NPOHJUUV-vis-NIRZ_Y[b(KBr disk, D7).
Figure 3 apH2 (F,), apH– (6,), A� 1 (>,), FeII(ClO4)2·6H2O (D,)PMeOH*'GHTQMeOH*�PS(+,)RP�-�!P&50/?P!B�3.
No. HD
*
* MeOHα
H * *
MeOHMeOH * HCHO HCO2H
*
1 350 ± 10 nm 24 hGC HD
(Figure 4g)
MeOH
Scheme 3
O–H(apH2) N–H(apH– 1)MeOH α
·CH2OH (H·) * (J. Phys. Chem. 1974, 78,
686-691.) *
MeOH* * Fe(II)
1 apH2 apH–
*
O
N O
NFeII
H2
H2 O
O
HH3C
H CH3
O
N O
NFeII
O
O
HH3C
H CH3
*
O
N O
NFeII
O
O
HC
H CH3
H2
H2
H2
HH
H2
O
N O
NFeII
O
O
H2C
H CH3
H2
H2
hv(289 nm)
π−π∗1HCHO
MeOH
H2
O
NH2hv
(289 nm)
O
NH2 *
π−π∗
O
NHH C
OH
H
H2
apH– MeOHHCHOH2
O
NH2
a)
b)
c)
H
H CO
H
H
H2
hv(289 nm)
MeOHHCHOH2
OH
NH2
OH
NH2 *
π−π∗apH2
Scheme 3. (a) apH2, (b) apH–, HTQ(c) A�1P�<�1MeOH8&5� �P�� �%#.
Figure 4. $)XZHTQ�&50/ �PGC: (a) H2$)XZ, (b) HDHTQD2$)XZ, (c) H2, HD, HTQ D2$)XZ, MeOH-d3�NP(d) apH2, (e) apH–, HTQA�1R�-�(λ = 289 ± 10 nm (200 W, t = 24 h))V:MLCP0/XZ, (f) A�1R�-�(λ = 350 ± 10 nm (200 W, t = 24 h))V:MLCP0/XZ.