1. Current Research Interests
(i)
Activation of Chemical Bonds by Transition-Metal Complexes (1, 3)
(ii) Metal Complexes Involved
in Multi-Step Electron Transfer Reactions in Biological Systems (2, 3)
(iii) Thiophene-Based
Functional Materials (1, 2)
(iv) Molecular Switching
Materials: Structural, Magnetic, and Catalytic Properties (5)
(1) Reactions of
Thiophene-Based Materials. Metal-mediated activation of strong
bonds, such as C−C, C−H, C−O, and C−X (X = halogen), is a vital research
area related to the catalytic transformation of organic molecules. Carbon-sulfur bonds are also activated on
metal centers to provide useful reaction pathways for novel
sulfur-containing compounds. The C−S
bond cleavage of thiophenes is an industrially important process in
catalytic hydrodesulfurization (HDS) that removes sulfur from organosulfur
compounds in petroleum feedstocks. The reactions of dibenzothiophenes
(DBT) with organometallic compounds are of particular interest because dibenzothiophenes are especially resistant to
desulfurization, which causes serious problems for further HDS. However, the rich sulfur-metal chemistry
originating from HDS would provide new ways to produce S-containing
functional materials.
We have used
pyridyl-substituted dibenzothiophenes,
4-(2′-pyridyl)dibenzothiophene (PyDBT) and its derivatives, as ligand precursors in
order to facilitate the metalation reaction. For example, the reaction of PyDBT with [Ru3(CO)12]
gave the diruthenium(II) complex [Ru(μ-PyBPT-κ3N,C,S)(CO)2]2,
where PyBPT denotes a dianion of
3′-(2′′-pyridyl)-1,1′-biphenyl-2-thiol (Figure 1). The N,C,S-tridentate
ligand PyBPT provides a pincer structure
consisting of two metallacycles. The precoordination
of the pyridyl group, including the N,S-chelating
mode, accelerates the oxidative addition of the C-S bond by increasing the
accessibility of the C−S bond to the vacant site on the metal center.
Figure
1. Formation of
thiolate-containing pincer structures by C–S bond cleavage.
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Another way to utilize C−S
cleavage reactions is modification of C−S cleaved ligands in
transition-metal complexes. A
thiolate-bridged diiron carbonyl complex
derived from benzothiophene, [Fe2(μ-SC6H4CHCH)(CO)6], which
was reported by Rauchfuss et al. (Organometallics,
1988, 7, 1171), reacted with
terminal alkynes under photoirradiation conditions to afford diiron carbonyl complexes of p-conjugated
thiolate ligands as alkyne insertion products (Figure 2). Various functional groups were
introduced on the extended carbon chain.
This reaction process involves insertion of CO and/or migration of
coordinating functional groups via C−N or C−O bond cleavage.
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Figure
2. Reactions of a diiron
complex containing C-S cleaved benzothiophene with alkynes.
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(2) Mimics of [FeFe]-Hydrogenase Active Sites. Thiolate iron complexes are
found in the active site of hydrogenases, which catalyze the formation and
consumption of dihydrogen in biological systems. The active site of [FeFe]-hydrogenases
consists of a diiron center bridged by a
dithiolate ligand and a {4Fe4S} cubane cluster. The diiron
center has carbonyl and cyanide ligands, and one of the two Fe ions is
connected to the {4Fe4S} cluster via a cysteinyl residue (Figure 1a). A
binding site for substrates is in the diiron
unit, and the {4Fe4S} cluster is involved in electron transfer in the
catalytic cycle of [FeFe]-hydrogenases.
We
synthesized a thiolate-bridged diiron carbonyl
complex [{Fe(μ-PyBPT-κ3N,C,S)(CO)2}Fe(CO)3]
by the photochemical reaction of PyDBT with
[Fe(CO)5] (Figure 1b). An Fe(CO)3 unit in the PyBPT complex is bound to the thiolate-containing
metallacycle to form a carbon- and sulfur-bridged dinuclear structure with
an Fe−Fe bond, which is similar to the diiron
unit of the [FeFe]-hydrogenase active site. The C,S-bridged diiron complex and its Schiff base and oxazoline
derivatives showed electrocatalytic ability for
proton reduction.
Figure 3. Structures of (a) the active site of [FeFe]-hydrogenases in the
oxidized state and (b) a diiron complex with an
S,C,N-tridentate ligand.
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(3) N2 Activation. Biological reduction of dinitrogen to
ammonia is catalyzed by nitrogenase enzymes under ambient conditions,
which is an essential process in the biochemical nitrogen cycle. The N2 binding and reduction
proceed at the FeMo-cofactor in nitrogenase, in
which the iron centers are surrounded by the sulfur donor atoms. The structure of the FeMo-cofactor has been revealed by crystallographic
studies, and synthetic approaches are currently underway to obtain the
structural model. In addition, the
reduction and functionalization of the coordinated N2 using
early- to middle-transition-metal complexes have become an active
research area. However, the
mechanistic details of the N2 reduction on the FeMo-cofactor are still unclear.
We recently reported that sulfur-bridged Ta2M2
complexes (M = Mo, Cr) containing a four-electron-reduced dinitrogen
ligand, [Cp*Ta(μ-SC6H4Me)2M(CO)4]2(μ-η1:η1-N2)
(Cp* = η5-C5Me5),
were synthesized from the ditantalum complex
[Cp*Ta(SC6H4Me)2]2(μ-η1:η1-N2),
which was obtained by a one-pot reaction using [Cp*TaCl4], di-p-tolyl disulfide, and KC8
under dinitrogen (Figure 4). Crystal structures of the Ta2 and
Ta2M2 complexes revealed the analogy of the
Ta–N–N–Ta moieties. This new
synthetic procedure provides various types of S-bridged multinuclear N2
complexes, which should be useful for investigating the reactivity of N2
incorporated in sulfur rich metal clusters.
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Figure
4. Structure of S-bridged Ta2M2
complexes with N24– (M = Mo, Cr).
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(4) Mimics of Oxygen
Evolving Center in Photosystem II. Photosynthetic water oxidation is
catalyzed by the oxygen evolving complex (OEC) in photosystem II
(PSII). X-ray diffraction studies of
PSII revealed that the active site of the OEC has a Mn4CaO5
cluster. A variety of tetranuclear
manganese clusters were synthesized to model the OEC active site, and their
structural, spectroscopic, and magnetic properties were investigated. We recently designed 5,5′-(9,9-dimethylxanthene-4,5-diyl)bis(salicylaldehyde)
(H2xansal). The xansal-based Schiff base ligands secure two Mn ions in
close proximity. This bimetallic platform
is applicable to the tetrametallic one by
dimerization. We synthesized Mn4
complexes by using a xansal-based ligand derived
from H2xansal and 3-amino-1-propanol. Figure 5 shows an acetate-bridged Mn4
complex, which has an incomplete double-cubane structure of Mn4O6. This complex is a potential starting
material for the model of the OEC active site, because the defective site
could be occupied by a Ca2+ ion to form a Mn3CaO4
cubane structure binding a fourth Mn ion.
Figure
5. Structure of a tetramanganese(II,II,III,III)
complex supported by xanthene-bridged Schiff base ligands.
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(5) Multimetallic Catalysts. Chiral sulfoxides are useful building
blocks in asymmetric synthesis of organic compounds. Enantioselective oxidation of sulfides
catalyzed by transition metal complexes is an efficient method to prepare
chiral sulfoxides. In the last two
decades, metal complex catalysts containing chiral salen-type
Schiff base ligands have been developed for the asymmetric sulfoxidaiton reactions, showing moderate to high
enantioselectivity. On the other
hand, chiral multimetallic complexes have
recently been designed as efficient asymmetric catalysts which cause
proximity effect. If two metal
centers in a catalyst act as an enantioselective Lewis-acid center to catch
a sulfide and as an enantioselective oxidation site, respectively, the
sulfide is expected to be oxidized to the corresponding chiral sulfoxide in
high enantioselectivity by the cooperative effect.
Several
dimeric salen-type complexes, in which the
monomeric units are connected by organic linkages, have been synthesized,
and their catalytic properties have been investigated. However, structurally characterized salen-type complex dimers with a face-to-face
arrangement are very rare. We have
synthesized an optically active dinuclear manganese(III)
complex with a cyclic ligand, in which two salen-type
units are anchored by two 9,9-dimethylxanthene-4,5-diyl spacers (Figure
6). The chiral dimanganese complex
was found to have a face-to-face structure in close proximity and showed
catalytic activity for the asymmetric oxidation of sulfides by
iodosobenzene. The
enantioselectivity was improved by the addition of 4-(dimethylamino)pyridine (DMAP) to the reaction system, which was not
effective for the corresponding mononuclear catalyst.
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2.
Selected Publications
1.
“Skeletal
Modification of Benzothiophene Mediated by Iron Carbonyls: Insertion of
Terminal Alkynes with Migration of Amino and Alkoxy Groups” Kyohei
Kobayashi, Masakazu Hirotsu, Isamu
Kinoshita, Organometallics, 2013, 32 (18), 5030-5033.
2.
“Titanium and manganese complexes supported by a xanthene-bridged
bis(tripodal N2O2) ligand: isomerization,
intramolecular hydrogen bonding and metal-binding ability” Masakazu Hirotsu,
Keisuke Kawamoto, Rika Tanaka, Yuji Nagai, Keiji Ueno,
Yoshio Teki, Isamu Kinoshita, Dalton Trans.,
2013, 42 (34), 12220-12227.
3.
“Carbon-
and Sulfur-Bridged Diiron Carbonyl Complexes
Containing N,C,S-Tridentate Ligands Derived from
Functionalized Dibenzothiophenes: Mimics of the [FeFe]-Hydrogenase Active Site” Masakazu Hirotsu, Kiyokazu
Santo, Hideki Hashimoto, Isamu Kinoshita, Organometallics, 2012,
31 (21), 7548-7557.
4.
“Design, synthesis, magnetic properties of a p-radical ligand with photo-excited high-spin state and its Fe(II) complex. The first stage of a new strategy for
LIESST materials.” Koichi Katayama, Masakazu Hirotsu,
Isamu Kinoshita, Yoshio Teki, Dalton Trans.,
2012, 41 (43), 13465-13473.
5.
“Anion-Controlled Assembly of Four Manganese Ions: Structural,
Magnetic, and Electrochemical Properties of Tetramanganese Complexes
Stabilized by Xanthene-Bridged Schiff Base Ligands” Masakazu Hirotsu,
Yuu Shimizu, Naoto Kuwamura,
Rika Tanaka, Isamu Kinoshita, Ryoichi Takada, Yoshio Teki,
Hideki Hashimoto, Inorg. Chem., 2012, 51 (2), 766-768.
6.
“Sulfur-Bridged Ta-M (M = Mo, Cr) Multinuclear Complexes Bearing a
Four-Electron-Reduced Dinitrogen Ligand” R. Takada, M. Hirotsu, T. Nishioka, H.
Hashimoto, I. Kinoshita, Organometallics,
2011, 30 (16), 4232-4235.
7.
“Carbon–sulfur bond cleavage reactions of dibenzothiophene
derivatives mediated by iron and ruthenium carbonyls” M. Hirotsu,
C. Tsuboi, T. Nishioka,
I. Kinoshita, Dalton Trans., 2011, 40 (4), 785-787.
8. “Manganese(II), Nickel(II), and Palladium(II) Complexes
of a Terpyridine-Like Ligand Containing a Sulfur Linkage, and an Analogous
NCN Pincer Palladium(II) Complex: Synthesis, Characterization, and
Pd-Catalyzed Reactions” M. Hirotsu, Y. Tsukahara, I.
Kinoshita, Bull. Chem. Soc. Jpn., 2010,
83 (9), 1058-1066.
9.
“Synthesis and characterization of xanthene-bridged Schiff base
dimanganese(III) complexes: bimetallic catalysts for asymmetric oxidation
of sulfides” M. Hirotsu, N. Ohno, T.
Nakajima, C. Kushibe, K. Ueno, I. Kinoshita, Dalton Trans., 2010, 39 (1),
139-148.
10.
“Steric, geometrical and solvent effects on redox potentials in salen-type copper(II) complexes” M. Hirotsu,
N. Kuwamura, I. Kinoshita, M. Kojima, Y.
Yoshikawa, K. Ueno, Dalton Trans.,
2009, (37), 7678-7683.
11. “Ruthenium and Rhodium Complexes with
Thiolate-Containing Pincer Ligands Produced by C-S Bond Cleavage of
Pyridyl-Substituted Dibenzothiophenes” M. Shibue, M. Hirotsu, T.
Nishioka, I. Kinoshita, Organometallics, 2008,
27 (17), 4475-4483.
12.
“A Thiacalix[3]pyridine Copper(I) Complex
as a Highly Active Catalyst for the Olefin Aziridination
Reaction” Y. Tsukahara,
M. Hirotsu, S. Hattori, Y. Usuki, I. Kinoshita, Chem. Lett.,
2008, 37 (4),
452-453.
13. “Extreme N-N Bond Elongation and Facile N-Atom
Functionalization Reactions within Two Structurally Versatile New Families
of Group 4 Bimetallic “Side-on-Bridged” Dinitrogen Complexes for Zirconium
and Hafnium” M. Hirotsu, P. P. Fontaine, P. Y. Zavalij,
L. R. Sita,* J. Am. Chem. Soc., 2007, 129 (42), 12690-12692.
14. “Dinitrogen Activation at Ambient Temperatures: New
Modes of H2 and PhSiH3 Additions for an
“End-On-Bridged” [Ta(IV)]2(m-h1:h1-N2)
Complex and for the Bis(m-nitrido) [Ta(V)(m-N)]2
Product Derived from Facile N-N Bond Cleavage” M. Hirotsu, P. P.
Fontaine, A. Epshteyn, P. Y. Zavalij,
L. R. Sita,* J. Am. Chem. Soc., 2007, 129 (30), 9284-9285.
15. “Synthesis of a Cofacial Schiff-Base Dimanganese(III) Complex for Asymmetric Catalytic
Oxidation of Sulfides” M. Hirotsu, N. Ohno, T.
Nakajima, K. Ueno, Chem. Lett., 2005, 34 (6), 848-849.
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