202019

June 2019
Issue #20

CONTENTS
Integrated Research Consortium on
Chemical Sciences . . . . . . . . . . . . . . . . . . . . . . . . . . .
Core-to-Core Program . . . . . . . . . . . . . . . . . . . . . . .
Research Topic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Visiting Professors 2018 . . . . . . . . . . . . . . . . . . . . . .

2
4
6
8

Report from the Chemical Instrumentation
Facility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Chemistry Gallery . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Retirement Address . . . . . . . . . . . . . . . . . . . . . . . . . .
Farewell Party . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
RCMS Seminars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

11
12
13
14

Awards 2018 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Staff List . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

This newsletter is also available in PDF format from the RCMS homepage (ihttp://www.rcms.nagoya-u.ac.jp/).

RCMS NEWS

Integrated Research Consortium on Chemical Sciences
2018
In 2018, IRCCS, Integrated Research Consortium on Chemical Sciences, a pioneering synthesis of a new scientificbase and nurturing the next generation of researchers (Hokkaido University Institute for Catalysis, Nagoya University
Research Center for Materials Science, Kyoto University International Research Center for Elements Science Institutefor Chemical Research, Kyushu University Institute for Materials Chemistry and Engineering) held the symposium
below.

The 2nd Young Researchers Forum
Chitose city, Hokkaido, June 15-16, 2018

Group photo＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊The 2nd International Symposium“New Future by Chemical Synthesis and Energy Materials”
Kyoto University, January 25-26, 2019

Director, Prof. Tatsumi

Prof. Yasuhiro Tachibana

2

The 4th Symposium＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊

Kyushu University, October 29-30, 2018

Prof. Tomooka

Prof. Yanai

Group photo＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊

Prof. Durrant

Group photo

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RCMS NEWS

Core-to-Core Program“Elements Function for Transformative Catalysis and Materials”
2014 - 2018
As part of the Core-to-Core Program “Strategic Research Networks (Type A)” operated by the Japan Society
for the Promotion of Science (JSPS), the program “Elements Function for Transformative Catalysis and Materials”
is promoted by the Research Center for Materials Science and the Department of Chemistry, Graduate School of
Science at Nagoya University, with Professor Shigehiro Yamaguchi serving as Project Coordinator. In this program,joint research and dispatch of researchers is actively performed with the participating institutions at the University of
Munster (Germany), the Technical University of Berlin (Germany), Queen’s University (Canada), and Kyoto University(Japan).
The Core-to-Core Program has enabled the deployment of master’s students, and outstanding young researchers expected to perform globally in the future can now be refined through participation in international joint
research performed overseas at an early stage.
The 2018 academic year was the last year of this program. The final joint Symposium featured with GTR;
Graduate Program of Transformative Chem-Bio Research at Nagoya University.

Prof. Nakamura

Prof. Crudden

4Prof. Glorius

Prof. Yamaguchi

Prof. Saito

Group photo

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RCMS NEWSResearch Topic(Molecular Catalysis)

Mechanistic Study of Asymmetric Hydrogenation of
Sterically Demanding Ketones using PNN–Ru complex
A ruthenium complex having a linear tridentate

ketone is significantly affected

sp 3P/sp 3NH/sp 2N ligand PN(H)N ((R)-2’-(diphenyl-

by [CH3OK]0, showing a char-phosphino)-N-(pyridin-2-ylmethyl)[1,1’-binaphthalen]-acteristic curve with a peak

2-amine) efficiently hydrogenates both nonchelatablefollowed by a pseudo-minus-

and chelatable sterically-demanding ketones underfirst-order decay. The RuNH is

the presence of a catalytic amount of CH3OK with higheasily deprotonated by CH3OK

enantioselectivity in CH3OH–DMSO solvent (Figure 1)

to generate RuNK, which is

.

[1,2]

less reactive but has the sameenantioselectivity. Increased contribution of the slow
RuNK cycle decreases the rate at higher [CH 3OK] 0.
The RuNH- and RuNK-involved dual catalytic cycle issupported by curve-fitting analyses and K+ trapping experiments (Figure 2)[3]. In hydrogenation of b-keto ester
as functionalized ketone, only the RuNH cycle operates
because the substrate is preferentially deprotonatedover RuNH.

Figure. 1. Caatalytic asymmetric hydrogenation of sterically demanding
ketones using PNN-Ru compiex.

The complex exclusively forms fac-[Ru(PN(H)N)(dmso)3](BF4)2 (A) over the mer isomer with the help of
the three strongly p-accepting DMSO ligands. The threedifferent ligating atoms exert a divergent effect on thetrans-DMSO—Ru bond strengths. This enables the stereoselective generation of fac-RuH(CH3O)(PN(H)N)- (dmso)(RuNH). The reaction proceeds at the H—sp3N—Ru—H

Figure. 2. Dual catalytic cycle.

bifunctional reaction site of fac-RuH2(PN(H)N)(dmso),
and high enantioselectivity is attained in a chiral 3D

References

cavity constructed by the sp3N trans DMSO, the confor-[1] ‌T. Yamamura, H. Nakatsuka, S. Tanaka, M. Kitamura,mation of which is fixed by a PyC(6)H—O=S hydrogenbond. We determined the structures of RuNH, the K
amide RuNK, Ru dihydride, and Ru amido species bydetailed NMR analysis using 15N-labeled PN(H)N andC(3)-Ph-substituted PN(H)N.

[3]

The reaction rate of hydrogenation of simple

6

Angew. Chem. Int. Ed. 2013, 52, 9313–9315.
[2] ‌T. Yamamura, S. Nakane, Y. Nomura, S. Tanaka, M.
Kitamura, Tetrahedron 2016, 55, 3781–3789.
[3] ‌S. Nakane, T. Yamamura, S. K. Manna, S. Tanaka, M.
Kitamura, ACS Catal. 2018, 8, 11059–11075.
(Assistant professor, Shinji TANAKA)

Research Topic(Functional Materials)

Accurate wave function theories for large,
real-life molecules
Molecular properties such as electronic energy, dipole
moment and electron density are solely determined byknowing quantum mechanical behavior of the electrons
in the molecule itself. To this end, the only thing we haveto do is just to solve the Schrödinger equation for this“many-electron system” in the electric field created by thespatially-clamped nucleus. However, as predicted by Dirac
in 1920s [1], the many-electron Schrödinger equation is socomplicated that, even with the power of modern supercomputers, the exact and analytical solutions have neverbeen possible to obtain. Due to this Dirac’s nightmare,quantum chemists have put tremendous efforts to develop
accurate approximation schemes for calculating molecularelectronic structures in a reasonable computational time.
Amongst them, the density-functional theory (DFT) has
become a widely-accepted tool not only by computational
chemists but also by experimental chemists. In order tomodel the electronic structure of molecules with quantitative accuracy, inclusion of the correlation effect plays acentral role. My primary interest consists in development
and application of efficient and accurate electronic structure theories for large, real-life molecules.
In the Max-Planck-Institute, under the supervision ofProf. Dr. Frank Neese, we developed an accurate and nearlinear scaling wave function theory named domain-based
local pair-natural orbital coupled- cluster (DLPNO-CC)
theory [2]. The CC theory has been one of the most accurate
electronic structure theories. However, due to the steep
computational scaling with respect to the molecular size,
the applicability has been limited only to approximately
10 atoms. In DLPNO-CC scheme, which belongs to the
local correlation theories, short-range nature of dynamic
electron correlation is exploited to achieve reduced-scaling
computational costs. As can be seen from Figure 1, CPU
times spent for solving the DLPNO-CC equation are approximately 40 % of that for DFT calculation accelerated
resolution-of-the-identity algorithm (RI-DFT). The DLPNOCC methods have been extended to open-shell moleculesand shown applicable to real-life molecules composedof several hundred atoms independent of its spin-state.
Moreover, we have developed a linear-response theory
in the DLPNO-CC framework and succeeded to enableaccurate computation on various magnetic and electronic
properties [3]. We used the DLPNO-CC methods to calculate
the conduction properties of carbon nanotubes and succeeded to obtain good agreement with the experimental
values [4].

Currently, as a member ofdivision of functional materials,
I am working on development
and application of accurate andefficient electronic structure theory for large, highly-correlated
systems such as realistic activesite model of metalloenzymes.
Combination of ab initio density
matrix renormalization group(DMRG) theory as a static correlation solver and the local
correlation scheme for the remaining dynamic correlation
plays a key role.

Figure 1. Computational timings of DLPNO-CCSD in comparison to thatof DFT accelerated by resolution-of-the-identity algorithm.

Figure 2. Benchmarking DLPNO-CCSD against conventional CCSD andvarious DFT functionals.

References[1] P. A. M. Dirac, Proc. Royal Soc. A 123, 714 (1929).
[2]	M. Saitow, U. Becker, C. Riplinger, E. F. Valeev, F. Neese,J. Chem. Phys. 146, 164105 (2017).
[3]	‌M. Saitow, F. Neese, J. Chem. Phys. 149, 034104(2018).
[4]	M. Saitow, A. K. Dutta, F. Neese, Bull. Chem. Soc. Jpn.
92, 170 (2018).
(Assistant professor, Masaaki Saiow)

7

RCMS NEWS

Visiting Professor 2018
Assoc. Prof. Franklin (Feng) Tao
Associate Professor
University of Kansas, U.S.A.
Period of Stay: June 5, 2018 – July 24, 2018
Research Theme:
“Operando characterization of heterogeneous
catalysts”
Since June 4th, 2018, Prof. Franklin (Feng) Tao, an associate professor of Kansas University, USA,visited RCMS for the collaborative work on operando characterization of heterogeneous catalysts
for 2 months. Prof. Tao is one of the top young scientists in the fields of heterogeneous catalysis andsurface science. He discussed on recent progresses on operando characterization techniques using
hard X-rays at synchrotron facilities and started new collaborative works on operando XAFS imaging
and hard X-ray ambient pressure XPS (HAXPES) analysis of heterogeneous bimetallic catalysts.
During his stay at RCMS, he joined group seminars at the laboratory of inorganic chemistry anddiscussed with young researchers and graduate students. He also visited various laboratories at department of chemistry and department of chemical engineering at Nagoya university and discussed withvarious researchers in the departments. On 2nd July, he had an IGER-RCMS seminar “Road to Smallest
Bimetallic Catalysts” on the design, characterization, and remarkable catalysis of single-atom catalysts
and contributed education and research at Nagoya university.
At Pacifichem congress in 2020, we are organizing a symposium on in-situ and operando studiesof spectroscopy, microscopy, and catalysis for chemical and energy transformations together andhave continuous collaborations.

Professor 2018
Prof. Kaoru Yamanouchi
Professor,
Graduate School of Science, Univ. of Tokyo

Prof. Kaoru Yamanouchi graduated from Department of Chemistry, School of Science, The University of Tokyo in 1981, and received Doctor’s Degree from the same department in 1986. In 1985,
he was appointed as Research Associate at Department of Pure and Applied Sciences, College of Arts
and Sciences, The University of Tokyo, and was promoted to Associate Professor in 1990. Since 1997,
he has been Professor of Chemistry at Department of Chemistry, School of Science, The University ofTokyo. For more than 20 years, Professor Yamanouchi has been investigating atoms and moleculesinteracting with intense laser fields for exploring frontiers in ultrafast intense laser science.

8

Visiting Professor 2018
Prof. Lahcène Ouahab
Professor
Chemical Institute of Rennes, CNRSPeriod of Stay:January 8, 2019 – February 27, 2019
Research Theme:
Research on Molecular Magnetism
Prof. Lahcène Ouahab from the Chemical Institute of Rennes, France, stayed as a vising professor
in RCMS for two months since the beginning of January, 2019, working on the research of molecularmagnets. He has been working in this field for many years and is well known as the organizer of theInternational Conference on Coordination Chemistry (ICCC) at Brest, France, in 2016, During his stay,
we collaborated on synthesis of novel molecular magnets and their application to organic electronics
and spintronics.
In Nagoya University, he attended to the group meetings of the Awaga group, and visited many
chemistry laboratories in the Schools of Science and Engineering, giving valuable advices to students
and young researchers. He was full of curiosity and had an interest in everything. He gave an IGER-RCMS
seminar, “Lanthanides Complexes containing TTFs Ligands : Single Molecule Magnet behaviour andLuminescence” on Feb. 15th, in which we had good discussion. With a lot of good memories in Japan,
he returned to France on Feb. 27th, 2019.

9

RCMS NEWS

Report on the Chemical Instrumentation Facility
The Chemical Instrumentation Facility (CIF) is a
facility shared by the whole university that contains
instrumental analysis equipment including a nuclear
magnetic resonance (NMR) spectrometer, mass spectrometer, and spectroscopic analysis equipment foranalyzing molecular structures. In the CIF, services areprovided to users including teaching faculty, researchers, and students through maintenance of thesemeasurement instruments, lectures on measurement
methods, consultations for specific measurements, andentrusted measurement. At the end of fiscal 2018, Two
Mass spectrometers of ESI-Q-TOF-MS (compact, Bruker)
and MALDI-TOF/TOF-MS (ultrafleXtream, Bruker) wereintroduced to CIF with the cooperation of Graduate
Program of Transformative Chem-Bio Research (Program
Coordinator: Prof. Shigehiro Yamaguchi). These new
MSS enabled to conduct higher sensitive and accurate
MS measurement. During the 2018 fiscal year, as shownin “CIF Utilization Status”, 68 research groups from theuniversity registered to use the facility, and the numberof teaching faculty, students, and researchers who
registered to use the facility during the year was 757.

Training session of atomic absorption spectrometer (Z-5710, HITACHI)[CIF Utilization Status]
Utilization Status for the Academic Year 2018
(April 2018 – March 2019)

Number of Uses/Measurements by Instrument

ESI-Q-TOF-MS (compact, Bruker)

MALDI-TOF/TOF-MS (ultrafleXtream, Bruker)

10

Utilization Status by Department(Total: 74 Groups, 746 People)

Chemistry Gallery
The Chemistry Gallery (2nd Floor of the Noyori Materials Science Laboratory ) welcomed many visitors again
in the 2018 academic year.
A particularly large number of visitors were welcomed during the following periods when Nagoya University
was open to the public.
   Number of visitors during Open Campus : 808 (August 8 to 10)   Number of visitors on Homecoming Day : 720 (October 20)
At the Chemistry Gallery, guest can experience Dr. Noyori’s sincere commitment, philosophy and passion thatearned him the Nobel Prize, the gratest honor for a scientist. There is also a message to the next generation fromDr. Noyori. Symbolical words from Dr. Noyori’s research handing down the profound mystery of Chemistry and theattitude of a genuine scientist of future chemists.

Prof. Noyori visited Chemistry Gallery to say hello to visitors.

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RCMS NEWS

Retirement Address
Professor Yoshihito Watanabe
Professor Yoshihito Watanabe, who retired on March 2019, gave his final lecture at the Lecture Hall in the Noyori
Materials Science Laboratory at 16:30 on Tuesday, March 12, 2019. In addition to faculty members of Departmentof Chemistry, Graduate School of Science and Research Center for Materials Science, a large number of participants
inside and outside the university gathered at the venue and listened intently to Professor Watanabe’s final lecture.
In the lecture entitled “40 years with metalloproteins” Professor Watanabe talked about his research life andachievements so that participants from various backgrounds could understand them, going back to his studies as
an undergraduate student. It was impressive that Professor Watanabe, who has spent time of multiple universities
and research environments including both inside and outside of Japan, introduced various chapters that shaped
his research philosophy. At the end of the lecture, a flower bouquet was presented by a student from his laboratory,
and the final lecture was concluded with a big applause.
Since April 2019, he has been managing the university and carrying out research activities as a senior presidential advisor of Nagoya University and a director of Integrated Research Consortium on Chemical Sciences (IRCCS).
We appreciate his efforts in research and education.

12

Farewell Party
March 12, 2019, Chemistry Lounge, Noyori Materials Science Laboratory
Prof. Yoshihito Watanabe
Assistant Prof. Fumiaki Tomoike
Mrs. Masako Kitamura (Chemistry Department Office)From left to right; Mrs. Kitamura, Asst. Prof. Tomoike, Prof. Watanabe

Abe group

Watanabe group13

RCMS NEWSRCMS Seminars

April 23, 2018 Prof. Sukbok Chang(Center for Catalytic Hydrocarbon
Functionalization, IBS-KAIST, Korea)“Development of Direct C-H Amination
Reactions: Inner-versus Outer-Sphere Pathways”

May 21, 2018 Dr. Anant Kapdi(UGC-FRP Assistant Professor, Institute for
Chemical Technology, Mumbai, India)“Phosphatriazenes: Versatile Ligands for
Bioactive Molecules Modification via
Sustainable Palladium Catalysis”

14June 29, 2018 Dr. J. Olof Johansson(University of Edinburgh)“Femtosecond spin and charge dynamics inmolecular magnets”

July 2, 2018 Assoc. Prof. Franklin (Feng) TAO(Dept. Chem., Univ. Kansas)“ Road to Smallest Bimetallic Catalysts”

15

RCMS NEWS

July 27, 2018 Prof. Dr. Dmitry G. Gusev(Wilfrid Laurier University, Canada)“Catalytic hydrogenation and dehydrogenative
coupling”

December 3, 2018 Prof. Lionel Cheruzel(San José State University)“Hybrid P450 Enzymes Featuring
Ru(II)-diimine Complexes”

16December 4, 2018 Prof. Jaclyn Brusso(University of Ottawa)“Exploring Tunable Nanoscale Metal
Complexes Through Ligand Design”

December 17, 2018 Prof. Rinaldo Poli
(Université de Toulouse, UPS, INPT, France)“Mechanistic studies on ketone hydrogenationand transfer hydrogenation in the absence of
deprotonatable ligands:going beyond the
Noyori mechanism”

17

RCMS NEWS

February 15, 2019 Prof. Lahcène OUAHAB(Institut des Sciences Chimiques de Rennes)“Lanthanides Complexes containing TTFs
Ligands : Single Moleculemagnet behaviour and Luminescence”

18

Awards 2018

Assistant Prof. Haruka Omachi

Alexander von Humboldt Foundation Research Award
Prof. Shigehiro Yamaguchi, Director of RCMS, in the middle(March 29th, 2019 in Bamberg, Germany)

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RCMS NEWS

Staff List
Director

Professor

Special Advisor

University Professor Ryoji Noyori

Organic Synthesis Professor

Inorganic
Synthesis

Functional
Materials

Biomaterials
Research
Molecular
Catalysis

Collaborative
Studies

ChemicalInstrumentation
Facility

Shigehiro Yamaguchi

Shigehiro Yamaguchi(2291) yamaguchi@mbox.chem.nagoya-u.ac.jp(2291) yamaguchi@mbox.chem.nagoya-u.ac.jp

Assistant Professor Soichiro Ogi(5750)

ogi.soichiro@chem.nagoya-u.ac.jp

Assistant Professor Akiko Yagi

(5873)

yagi.akiko@d.mbox.nagoya-u.ac.jp

Professor

Mizuki Tada

(6200)

mtada@chem.nagoya-u.ac.jp

Associate Professor Hideo Takagi(5473)

htakagi@chem.nagoya-u.ac.jp

Associate Professor Yasuyuki Yamada(2471)

yy@chem.nagoya-u.ac.jp

Designated Professor Kazuyuki Tatsumi(2474)

i45100a@nucc.cc.nagoya-u.ac.jp

Professor(2494)

hishi@chem.nagoya-u.ac.jp

Akiyoshi Hishikawa

Assistant Professor Zhang Zhongyue(5106) zhangzhongyue@i.mbox.nagoya-u.ac.jp

Assistant Professor Haruka Omachi(3660) omachi.haruka@a.mbox.nagoya-u.ac.jp

Assistant Professor Masaaki Saitow(2851)

masa.saitow@chem.nagoya-u.ac.jp

Professor(3049)

p47297a@nucc.cc.nagoya-u.ac.jp

Assistant Professor Fumiaki Tomoike(2950)

tomoike@chem.nagoya-u.ac.jp

University Professor Ryoji Noyori(2956)

noyori@chem3.chem.nagoya-u.ac.jp

Assistant Professor Hiroshi Naka

(5411)

h_naka@nagoya-u.jp

Assistant Professor Shinji Tanaka(2960)

tanaka@os.rcms.nagoya-u.ac.jp

Yoshihito Watanabe

Guest Professor

Kaoru Yamanouchi (Professor, The University of Tokyo)

Guest Professor

Lahcène Ouahab (Professor, Chemical Institute of Rennes, CNRS)

Guest Associate
Professor

Feng Tao (Associate Professor, University of Kansas)

Manager / Professor Susumu Saito(5945)

saito.susumu@f.mbox.nagoya-u.ac.jp

Technical official

Yutaka Maeda(3069)

maeda@cic.nagoya-u.ac.jp

Technical official

Kin-ichi Oyama(3069)

oyama@cic.nagoya-u.ac.jp

International Advisory Board

Michael Grunze (Professor Emeritus, Heidelberg University)
Roald Hoffman (Professor Emeritus, Cornell University – Laureate, Nobel Prize in Chemistry)
Henri Boris Kagan (Professor Emeritus, Paris-Sud 11 University)
Atsuko Tsuji (Designated Professor, Nagoya University)

Cooperating
Faculty

RCMS Office20

Professor

Hisanori Shinohara (Graduate School of Science) (2482)

noris@nagoya-u.jp

Professor

Kenichiro Itami (Institute of Transformative Bio-Molecules) (6098) itami.kenichiro@a.mbox.nagoya-u.ac.jp

Professor

Masato Kitamura (Graduate School of Pharmaceutical Sciences) (2957)

kitamura@os.rcms.nagoya-u.ac.jp

Distinguished Invited Sumio Iijima
University Professor(6460)

iijimas@nagoya-u.jp

Administrative Staff Yuko Kihara(5907)

kihara@os.rcms.nagoya-u.ac.jp

Administrative Staff Sonoe Tankiku(5908)

tankiku@os.rcms.nagoya-u.ac.jp