No.1

26 172

: ��=@�^ad�(�����&5�9"�eE=@�c���5;��]W\`W\fP

/

* 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.