MOLCAT

2014 May 1
MOLCAT
Welcome to the Molecular Catalysis Research Team
WEB Site
Molecular Catalysis Laboratory
The Laboratory
Academic Staff:
Dr. Masafumi Hirano
PhD
Professor
Office: New 1 bldg. N514A
Phone & Fax: +81 423 887 044
Email: [email protected]
Dr. Nobuyuki Komine
D. Eng.
Research Associate
Office: New 1 bldg. N513
Email: [email protected]
Ms. Sayori Kiyota
MSc
Technical Staff
Office: New 1 bldg. N513
Email: [email protected]
Department of Applied Chemistry,
Graduate School of Engineering,
Tokyo University of Agriculture
and Technology, 2-24-16
Nakacho, Koganei, Tokyo 1848588, JAPAN
MOLCAT
Molecular Catalysis
Research Team
Tokyo Univ of A & T
Research Interests:
1. Cross-Dimerization of Alkenes: One of the major focuses in our lab is
the selective cross-dimerization of substituted alkenes by zero-valent
ruthenium complex. We have developed the first enantioselecive crossdimerization between substituted alkenes, that goes through an
oxidative coupling mechanism. (Org. Lett., 2013, 15, 2486)
2. Bond Activation by Internal Electrophilic Substitution Mechanism:
Interal Electrophilic Substitution (IES) mechanism, which is also named as
Concerted Metallation Deprotonation (CMD) or Ambiphilic Metal-Ligand
Activation (AMLA), is one of the current topics in bond activation
processes. However, the understanding in the molecular level and the
application is still limited. We have shown multiple C-H bond activation
processes of alkyl group in the ortho position of the aryloxo group.
(Organometallics, 2014, 33, 1235)
互換性や機能性、使い
やすさの向上
2
Research Interests:
3. Successive C-O/C-H Bond Activation of Esters: The C-H bond
activation by the Internal Electrophilic Substitution (IES) mechanism
normally starts from the oxidative addition of organic halide to the low
valent metal compound followed by the anion exchange between the
resulting halido and carboxylato (or carbonato) to give
(carboxylate)(organo)metal species. If we can make this species directly
from esters by the C-O bond activation, this process must be very
attractive from the atom and step economy point of view. We have
succeeded direct formation of fluorene by the C-O/C-H bond activation
process by a Pd catalyst. (Organometallics, 2014, 33, 1921)
4. Highly Active Catalyst for Hydrometallation: We recently found
the mono-phosphine Pd(0) compounds to be a highly active
hydrometallation catalyst under mild conditions. Hydrometallations,
particularly those using main group elements, are highly attractive for
the synthetic point of view.
3
Research Interests:
The MOLCAT
The molcat is a research team headed by
Masafumi Hirano at Tokyo University of A &
T. The molcat is interested in Molecular
Catalysis and Organometallic and
Coordination Chemistries.
Interested in becoming a MOLCAT?
Don’t hesitate to contact MH.
MOLCAT
Molecular Catalysis
Research Team
Tokyo Univ of A & T
METAL CHIC KS
The Metal chicks is an alumnae and alumni
organization of molcats.
The Keyaki Party
The united alumni organization involving
those of Prof. Emer. S. Komiya and Prof. A.
Fukuoka (Hokkaido U) is named Keyaki Party
(Zelkova).
4
Publication List
MOLCAT
Molecular Catalysis
Research Team
Tokyo Univ of A & T
●Nobuyuki Komine,* Makoto Abe, Ryoko Suda, Masafumi Hirano , Markovnikov-Selective
Hydrosilylation of Electron-Deficient Alkenes with Arylsilanes Catalyzed by
Mono(phosphine)palladium(0), Organometallics, 34, 432-437 (2015).
DOI: 10.1021/ om500927z
●Yuki Hiroi, Nobuyuki Komine, Sanshiro Komiya, Masafumi Hirano,* , Regio- and Enantioselective
Linear Cross-Dimerization between Conjugated Dienes and Acrylates Catalyzed by New Ru(0)
Complexes, Organometallics, 33, 6604-6613 (2014).
DOI: 10.1021/ om500927z
●Masafumi Hirano,* Takuya Okamoto, Nobuyuki Komine, Sanshiro Komiya, Stoichiometric
Formation of Conjugated Dienyl Ketones from 1,3-Dienes and Ketenes at a Ruthenium(0) Centre,
New J. Chem., 38, 5052-5057 (2014).
DOI: 10.1039/C4NJ01001A
●Masafumi Hirano,* Sosuke Kawazu, Nobuyuki Komine, Direct Access to Fluorene by Successive
C-O/C-H Bond Activations of 2-Phenylbenzyl Ester, Organometallics, 1921-1924 (2014).
DOI: 10.1021/om500341v
●Masafumi Hirano,* Yasuto Yanagisawa, Endin Mulyadi, Nobuyuki Komine, Sanshiro Komiya,
Multiple C-H Bond Cleavage of Alkyl Group in (2,6-Dialkylphenoxo)ruthenium(II) Complex,
Organometallics, 33, 1235-1244 (2014).
DOI: 10.1021/om5000248
●Nobuyuki Komine, Ayako Kuramoto, Kouhei Nakanishi, Masafumi Hirano, Sanshiro Komiya,*
Alkene and Alkyne Insertion into Hydrogen-Transition Metal Bonds Catalyzed by Palladium(0)
Complex, Topics in Catalysis, 57, 960-966 (2014).
DOI: 10.1007/s11244-014-0258-8
R
MLn
MLn
LnPd
R
H
rapid
R
R
MLn
rate-determining
step
LnPd
+
MHLn
rapid
OO
MHLn
MLn
R
F
H
LnPd
LnPd
L=PPh3
NC
OR
RE
CT
ED
PR
elimination form alkylpalladium intermediate. Although it 216
ide complex to give alkyl (or alkenyl)
is still not clear how MHCp(CO)3 enhances the reductive 217
h the reformation of hydridopalladimechanism is supported by the result
elimination process at present, some interaction between 218
●Masafumi Hirano,* Haruka Inoue, Takuya Okamoto, Takao Ueda, Nobuyuki Komine, Sanshiro
reaction of heterodinuclear methylthe dinuclear alkylpalladium species and MHCp(CO)3 219
Komiya, Xian-qi
Wang,
and Martin
A. Bennett,*
Cross-dimerization
between Different
um complex with MoHCp(CO)
.
The
would
oxidize
the Pd center
to promote reductive
elimi- cisoid220 and
3
nation. The insertion of alkyne into Mo–H or W–H bond 221
lpalladium–molybdenum complex,
transoid-1,3-Dienes at a Ruthenium(0) Center, New J. Chem. 37, 3433-3439 (2013).
CO)3 with MoHCp(CO)3 in C6D6 at
also catalyzed by palladium(0) complex. The present 222
DOI:
10.1039/c3nj00429e
results may provide a new route for alkene and alkyne 223
smoothly gave methylmolybdenum
CO)3 (41 %) and hydridepalladium–
insertion into stable transition metal hydrides.
224
x, (dppe)HPd–MoCp(CO)3 (22 %)1.
al-hydride significantly increases the
4 Experimental
addition of ethyl acrylate showed no
225
the reaction rate. Added triphenyl4.1 General
nhibits coordination of ethyl acrylate
226
to palladium center. Since all these
All manipulations were carried out under a dry nitrogen or 227
e reversible, organomolybdenum (–
argon atmosphere using standard Schlenk techniques. NMR 228
nese) complex is considered to be
solvent (C6D6) was commercially obtained and dried with 229
more stable than the corresponding
sodium wire. NMR spectra were recorded on a JEOL LA-300 230
spectrometer (300.4 MHz for 1H). Chemical shifts were 231
reported in ppm downfield from TMS for 1H. MoHCp(CO)3 232
[17], WHCp(CO)3 [18], MH(CO)5 [19], WDCp(CO)3 [20], 233
Pd(PPh3)4 [21] and Mo[CH(CO2Et)Me]Cp(CO)3 [11] were 234
alkynes insertion into Mo–H, W–H,
prepared by the literature methods with minor modifications. 235
zed by palladium(0) complexes were
All other chemicals were obtained from commercial sources 236
of alkenes such as ethyl acrylate and
and used directly without further purification.
237
drogen–metal bond smoothly gave
ovnikov-selective alkyl complexes.
4.2 Alkene and Alkyne Insertion into Hydrogen238
s from the selective migration of the
Transition Metal Bonds Catalyzed by
239
clear hydridepalladium complex into
Tetrakis(triphenylphosphine)palladium Complex
240
hyl acrylate and acrylonitrile to give
e alkylpalladium intermediate. The
As a typical procedure, reaction of molybdenum hydride 241
chiometric reaction show the imporwith t ethyl acrylate is given. Molybdenum hydride, Mo- 242
clear hydride complex in reductive
HCp(CO)3 and Ph3CH as an internal standard were placed in 243
an NMR tube. After addition of C6D6 and ethyl acrylate into 244
of electron density in the palladium center
this NMR tube, 5 mol% of Pd(PPh3)4 was added into the 245
bdenum complexes by the coordination of
mixture ([CH2 = CHCO2Et]initial = [MoHCp(CO)3]initial = 246
lts in acceleration of reductive elimination
0.0375 M). The reaction was monitored by 1H NMR, and 247
mplex.
NJC
Fig. 3 Molecular
diene-1,8-diyl)(Z4for clarity. Ellipsoid
Scheme 3 Cross-dimerisation between coordinated 2,3-dimethyl-1,3-butadiene and 1,3-dienes.
●Yuki Hiroi, Nobuyuki Komine, Sanshiro Komiya, and Masafumi Hirano,* Asymmetric
Cross-dimerization
betweenstructure
Methyl Methacrylate
andwhich
Substituted
The molecular
of 2da,
is Alkenes
shownbyin
Fig. 3, is
Ru(0)-Bicyclononadiene
Complex,
Org. Lett. 15,
2486-2489
(2013).2aa. The C(1)–C(3)
very similar to that
reported
for
complex
DOI:
10.1021/ol400963d
Z3-allylic
fragment, which has methyl groups at the 2- and
3-positions, has the supine-configuration, while the C(6)–C(8)
Z3-allylic fragment is prone. The C(4)–C(5) separation of
1.520(6) Å shows that these atoms are connected by a single
bond resulting from the coupling of the two diene units.
The 1H NMR spectrum of 2da in benzene-d6 contains a pair
of 3H singlets at d 1.74 and 1.82 due to the inequivalent methyl
groups on C(2) and C(3). A characteristic 1H triplet of doublets
at d 3.74 (J = 10.2, 7.0 Hz) can be assigned to the central methine
proton on C(7) in the prone Z3-allylic moiety, which is coupled to
6
( J = 10.5, 7.8 H
and syn-dispos
group at 9-CH
supine,syn-pron
tion of the coo
Cross-dimer
of the 2,5-dime
and (E)-1,3-pen
and syn-prone
(Scheme 4).
Surprisingly
predominantly
i.e., at the ste
(1) A),
dppe)
he acyl
mbered
he inscopito the
t (1JPe
d ethyl
trans
y this
transan the
cis-2urizaeffect,
etone.
iety of
bicyclo
ersion
iranes
etallic
Fig. 1. Three-dimensional representation of bridged species [(dppe)Pt(m-C(O)Np1kC,2kO)eMn(CO)4] (2) showing the numbering scheme. Thermal ellipsoids are shown
at the 50% probability level, except for hydrogen atoms, which are placed at the
calculated positions based on the riding model. Hydrogen atoms on the dppe and
●Matthew
T. Zamora,
Kenta
Oda, Nobuyuki
Komine,
Sanshiro
Komiya,*
methyl
groups
are not
shown.
Only the
ipso Masafumi
carbons Hirano,
of theand
dppe
phenyl
rings are
!
shown.
Relevant
parameters
(distances
in
A
and
angles
in
deg.):
PteMn
¼
2.607(1),
Stereoselective Thiirane Desulfurization Controlled by a Bridging or Terminal Acyl Ligand:
PteP(1) ¼ 2.284(2), PteP(2) ¼ 2.319(2), PteC(1) ¼ 2.022(8), MneO(1) ¼ 2.070(6),
Concerted vs SN2 Pathways, J. Organomet. Chem., 739, 6-10 (2013).
C(1)eO(1) ¼ 1.261(9);
P(1)ePteMn ¼ 169.97(5), P(2)ePteC(1) ¼ 173.9(3), PteMne
DOI:10.1016/j.jorganchem.2013.04.003
C(34) ¼ 167.3(3), O(1)eMneC(35) ¼ 176.1(3), MnePteC(1)eO(1) ¼ #0.3(5)
∆
∆
Scheme 3. Desulfurization of thiiranes using bridged (2) or non-bridged (4) species.
●Masafumi Hirano,* Ryo Fujimoto, Kohei Hatagami, Nobuyuki Komine, and Sanshiro Komiya,*
Stoichiometric Carbon-Hydrogen Bond Cleavage Reaction in a Bis(carboxylato)ruthenium(II)
Complex and Its Application to Catalytic H/D Exchange Reaction of Carboxylic Acids,
ChemCatChem, 5, 1101-1115 (2013).
DOI: 10.1002/cctc.201200686
●Masafumi Hirano,* Takuya Okamoto, Nobuyuki Komine, and Sanshiro Komiya
Stoichiometric Carbon-Carbon Bond Forming Reaction of 1,3-Diene with 1,2-Diene in a
Ruthenium(0) Complex, Organometallics 31, 4639-4642 (2012).
DOI: 10.1021/om300326q
●Masafumi Hirano,* Yasutomo Arai, Yuka Hamamura, Nobuyuki Komine, and Sanshiro Komiya
Stoichiometric and Catalytic Cross Dimerization between Conjugated Dienes and Conjugated
Carbonyls by a Ruthenium(0) Complex.
Straightforward Access to Unsaturated Carbonyl
Compounds by an Oxidative Coupling Mechanism, Organometallics, 31, 4006-4019 (2012).
DOI: 10.1021/om300234d
●Masafumi Hirano,* Yumiko Sakate, Haruka Inoue, Yasutomo Arai, Nobuyuki Komine, Sanshiro
Komiya, Xian-qi Wang, Martin A. Bennett,* Synthesis of Conjugated Diene Complexes of
4
Ruthenium(0) Derived
from Ru(η 6-naphthalene)(η
-1,5-COD): Z to E Isomerisation of
Author's
personal copy
Coordinated 1,3-Pentadiene, J. Organomet. Chem. 708-709, 46-57 (2012).
DOI:10.1016/j.jorganchem.2012.02.018
M. Hirano et al. / Journal of Organometallic Chemistry 708-709 (2012) 46e57
47
●Masafumi Hirano,* Masahiro Murakami, Toshinori Kuga, Nobuyuki Komine, and Sanshiro Komiya,*
Acid-Promoted sp3 C-H Bond Cleavage in a Series of (2-Allylphenoxo)ruthenium(II) Complexes.
Mechanistic Insight into the Aryloxo-Acid Interaction and Bond Cleavage Reaction,
Organometallics, 31, 381-393 (2012).
DOI: 10.1021/om200974c
was isolated as air-sensitive, thermally unstable brown crystals in
In an attempt to distinguish between these extremes, Müller
34% yield (Eq. (1)).
et al. [19] have employed the parameter Dd, which is the difference
between the average of the outer Ru"C (Ru"C(1) and Ru"C(4)) and
The crystalline solid could be stored under nitrogen at dry-ice
inner Ru"C (Ru"C(2) and Ru"C(3)) distances, and the C(1)"
temperature for a few weeks. Although the 1H and 13C NMR
spectra were in agreement with the formulation, elemental analRu"C(4) angle (a). For the diene form, Dd lies between "0.1
yses were not completely satisfactory owing to the instability and
and þ0.1 Å, and a between 75$ and 90$ . For 2a, the Dd and a values
are estimated to be þ0.009 Å and 79.33$ , respectively. Therefore,
sensitivity of the solid. After many attempts, a single-crystal of 2a
according to this analysis, the diene extreme is the main contribsuitable for X-ray analysis was finally obtained. The molecular
utor to the bonding in 2a.
structure of 2a is depicted in Fig. 1 and selected bond distances and
Similar complexes containing either acetonitrile or other nitriles
angles are listed in Table 2.
were obtained from 2,3-dimethylbutadiene (3aed), isoprene (4a,
The crystallographic analysis clearly shows a cisoid-h4-coordination of the 1,3-butadiene
fragmentHirano,*
at the Ru Shin-ya
centre. IfTatesawa,
the mid- Minoru
4c), (E)and (Z)-1,3-pentadiene
(E)-2-methyl-1,3-pentadiene
●Masafumi
Yabukami,
Yoko Ishihara,(5a),
Yusuke,
Hara, Nobuyuki
points of the olefinic double bonds are regarded as coordination
[(E)-6a, 6c, 6f] and 1,3-cyclohexadiene (7c). The benzonitrile
sites, the molecular structure
of 2aand
canSanshiro
be described
as beingCarbon-Hydrogen
a fivecomplexes
are slightly
more
stable than
those of acetonitrile or tKomine,
Komiya,*
Bond
Cleavage
Reaction
in Four-Coordinate
coordinate, approximately square pyramid, with the nitrile ligand in
butyl cyanide.
the axial position. It is(2,6-Dimethylbenzenethiolato)platinum(II)
similar to that observed in [Ru(h4-1,3,5Spectroscopic Dramatic
evidence shows
that the coordinated
Complexes.
Acceleration
by Thiolatonitriles are
C8H10)(h4-1,5-COD){P(OPh)3}] [16], [Ru(h4-C10H8)(h4-1,5-COD)(L)]
very labile. The EI-mass spectra do not show molecular ion peaks but,
] [13], and numerous
Fe(Organometallics,
h4-1,3-diene)(CO)330, 5110-5122
L ¼ PMe3, PEt3, P(OMe)3Hydrogen
for example,
a peak at m/z 291 in the spectra of the 2,3Acceptor,
(2011).
complexes [17,18]. The RueC distances to the 1,3-diene unit fall in
dimethylbutadiene complexes 3aed can be assigned to the fragDOI:
10.1021/om200345h
the range 2.176e2.191 Å
and are
similar to those observed in the
ment [Ru(C6H10)(C8H12)]þ and there are also intense peaks arising
6
4
from the nitrile. The IR spectra show a n(CN) band at ca.
compounds cited above and in [Ru(h -C6H6)(h -1,3-butadiene)]
19]. The distance C(2)eC(3) between the central atoms of the 1,32220e2240 cm"1, close to the value for the free nitrile
(2222e2260 cm"1) [20]. The red 1,4-phthalonitrile 2,3diene [1.421(5) Å] is the same as the terminal CeC distances
dimethylbutadiene complex 3d shows only one n(CN) band at
1.419(7), 1.416(5) Å] within the standard deviation, a pattern that is
2220 cm"1 (2234 cm"1 for free phthalonitrile), even though only one
generally similar to that observed in the Fe(h4-1,3-diene)(CO)3
complexes and different from the short-long-short pattern
of the CN groups is presumed to be coordinated. Although a dinuclear
observed in [Ru(h6-C6H6)(h4-1,3-butadiene)] [19]. The observed
structure bridged by 1,4-phthalonitrile is a possible alternative, the
pattern is consistent with the usual assumption of a minor contrielemental analysis of 3d clearly supports a mononuclear formulation.
bution to the metal-diene bond of an ene-diyl extreme (Chart 1).
Coordination of a nitrile through nitrogen usually causes an observable high frequency shift; a shift to lower frequency occurs only when
the metal centre has a strong back-bonding ability [21]. We assume
4
4
that the bands due to free and coordinated CN in 3d probably overlap.
3
1
The 1H NMR spectra of the acyclic 1,3-diene complexes show
3
1
resonances characteristic of h4-coordination at d ca. 0.5 and 1.7 due
2
2
N. Komine et al. / Journal of Organometallic Chemistry 696 (2011) 1927e1930
Table 1 (continued )
Entry
Substrate
Time
Product (ratio)
8b,c
7
68
b,d
7
393
13, 14
(98/2)
13, 14
(98/2)
9
10
48
11
48
Total yiel
16
0
0
15, 16
(!)
0
a
Reaction conditions: [RhCl(1,5-cod)]2 (0.025 mmol), PTA (0.15 mmol), allylic carbonate (0.50 mmol), acetylacetone (0.50 mmol), solvent ¼ water 2.0 mL, AcOEt 2.0
30 # C.
b
Reactions were carried out at room temperature.
c
PTA (0.10 mmol).
d
PTA (0.30 mmol).
these reactions. Cinnamyl carbonate (7) was less reactive in
The ratio of PTA to Rh was also important. When using 2 eq
comparison with crotyl derivative, but exclusively gave the
of PTA per mole of Rh, the yield of allylation products significa
branched allylation product (13) (Entry 7). Unusual effect of interdecreased in comparison with the result using 3 equivs of
face area on branch/linear ratio of the products by changing stirring
(Table 1, entry 8). On the other hand, addition of 6 equivs of PTA
speed was not observed in these reactions [2b]. On the other hand,
completely inhibited the reaction, suggesting the prior dissocia
trisubstituted allyl carbonate such as prenyl carbonate (8) showed
of PTA (Table 1, entry 9). The results suggest that active inter
no reactivity in this allylation reaction (Entry 10). Such a trend was
diate needs PTA as a ligand, but excess PTA compete with p
also observed
for allylicKomine,
acetatesMasafumi
(Entry 11).
These and
reactivity
coordination
of allyl carbonate.
●Yuki
Hiroi, Nobuyuki
Hirano*,
Sanshiro Komiya,
Prostereogenic
Face and
differences are probably due to the large steric hindrance of the
By analogy of previously reported branch-selective allylat
trisubstituted allylic
moiety,
discouragingOlefins
pre-requisite
coordinafollowing
mechanism
proposed for this catalytic allyla
Orientational
Control
of Coordinated
at Ru(0)
in Oxidative
Coupling
Reactionis between
tion of the C]C double bond to rhodium leading to a common
(Scheme 1) [2b]. An allylrhodium(III) species initially formed
allylrhodium
intermediate
which nucleophilicOrganometallics,
reaction of ace- 30,oxidative
addition
of allylic carbonate or acetate to Rh(I), follow
Methyl
Methacrylate
andto
2,5-Dihydrofuran,
1307-1310
(2011).
tylacetone takes place. Importance of prior coordination of C]C
by nucleophilic reaction of acetylacetone to give the correspond
DOI:
10.1021/om200091n
double
bond has been proposed [11]. The low reactivity of acetates
allylation product. Exclusive formation of the branched prod
compared to that of carbonate may be attributed to the difficulty in
from both 1-methylallyl and crotyl carbonates suggests
oxidative addition.
involvement of a common allylrhodium intermediate. It is unlik
3
●Nobuyuki
Kohtaro
Sachiyo Kanai,
Masafumi Hirano,
and h
Sanshiro
Komiya,*intermediate, since less-hinde
-allylrhodium(III)
We also Komine,
examined
some Ishiguro,
other water-soluble
phosphorus
to suppose
ligands for comparison and the results are also shown in Table 2.
side is generally allylated by the steric reason, though electro
H O/AcOEt biphasic system. Unfortunately the combinations with
other well-known water-soluble phosphine ligands such as TPPTS,
TPPMS, and tris(hydroxylmethyl)phosphine showed very low
DOI:10.1016/j.jorganchem.2010.10.037
catalytic activity.
[6d,12]. Initially formed h3-allylrhodium(III) probably rearrange
the h1-allylrhodium(III) by coordination of three trimethylph
phine ligands, where methyl substituents in the allylmetal in
mediate would stay in the remote position from Rh metal cente
Branch
Selective Allylation of Acetylacetone Catalyzed by Water-soluble
Rhodium Complex
effect of substitutents and ligand effect are also important fac
Use of DAPTA as ligands gave a similar selectivity and reactivity in
2
Catalyst,
J. Organomet. Chem. 696, 1927-1930 (2011).
●Masafumi Hirano, Yumiko Sakate, Nobuyuki Komine, Sanshiro Komiya, Xian-qi Wang, Martin A.
Bennett, Stoichiometric
Regio- and Stereoselective Oxidative Coupling Reaction of Conjugated
Dienes with Ruthenium(0).
A Mechanistic Insight into the Origin of Selectivity. Organometallics,
30, 768-777 (2011) .
DOI: 10.1021/om100956f
●Shin-ichi Tanaka, Nobuyuki Komine, Masafumi Hirano, and Sanshiro Komiya, Synthesis of
Heterodinuclear Ruthenium-manganese Complex Having mu-Benzylidene Ligand, J. Organomet.
Chem. 696, 632-635 (2011).
Author's personal copy
DOI:10.1016/j.jorganchem.2010.09.020
633
S.-i. Tanaka et al. / Journal of Organometallic Chemistry 696 (2011) 632e635
C(13)
C(5)
C(6)
C(12)
C(14)
C(4)
C(7)
C(11)
C(18)
C(19)
C(15)
C(10)
P(1)
C(17)
C(22)
C(16)
C(21)
C(20)
C(24)
C(3)
C(2)
C(26) C(27)
C(1)
O(1)
C(8)
C(30)
C(23)
C(9)
O(2)
O(4)
C(29)
C(42)
Mn(1)
C(48)
C(37)
C(28)
Cl(1)
C(47)
P(2)
C(38)
C(43)
O(3)
C(46)
C(31)
C(44)
Ru(1)
C(25)
O(5)
C(41)
C(40)
C(39)
C(45)
C(32)
C(36)
C(33)
C(35)
C(34)
Fig. 1. ORTEP drawing of 1. Selected bond distances (Å): Ru(1)-Mn(1) 2.6711(12), Ru(1)-Cl(1) 2.463(2), Ru(1)-P(1) 2.365(2), Ru(1)-C(1) 2.096(8), Mn(1)-Cl(1) 2.434(3), Mn(1)-P(2)
2.360(2), Mn(1)-C(1) 2.183(7). Selected angles (deg): Mn(1)-Ru(1)-Cl(1) 56.44(6), Mn(1)-Ru(1)-C(1) 52.86(19), Ru(1)-Mn(1)-Cl(1) 57.46(5), Ru(1)-Mn(1)-C(1) 49.9(2), Ru(1)-Cl(1)Mn(1) 66.10(6), Ru(1)-C(1)-Mn(1) 77.2(2).
2.3. Synthesis of (Cy3P)(OC)2Ru(m-CHPh)(m-Cl)Mn(CO)3(PCy3) (1)
þ
-
Na [Mn(CO)5] (254.4 mg, 1.167 mmol) was dissolved in THF
(8 ml). The solution was added to a THF (35 ml) solution of
RuCl2(PCy3)2(¼CHPh) (479.4 mg, 0.5825 mmol) at # 70 $ C. Then the
mixture was stirred for 3 h at # 20 $ C. All the volatile matter was
evaporated, and the resultant dark brown solid was extracted with
benzene (10 ml % 2). After removal of benzene in a vacuum, the
resultant dark reddish brown solid was recrystallized from THF/
hexane to give reddish brown crystals. Yield: 23% (133.4 mg,
0.1358 mmol). The vacuum dried crystals included a small amount
of solvents (0.15 THF and 0.12 hexane molecules/1) whose amounts
were estimated by 1H NMR. Anal. Calcd for C48H72ClMnO5P2Ru: C,
58.68; H, 7.39. Found: C, 59.00; H, 7.14. 1H NMR (C6D6, r.t.):
d 0.6e2.5 (m, 66H, PCy ), 6.88 (s, 1H, CHPh), 6.99 (t, J ¼ 7 Hz, 1H,
1
H NMR (C6D6, r.t.): d 2.07 (quint, JDH ¼ 2 Hz, CHD2), 6.99e7.07 (m,
o-Ph and p-Ph), 7.10e7.16 (m, m-Ph). 13C{1H} NMR (C6D6, r.t.):
d 20.76 (sept, JCD ¼ 19 Hz, CD3), 20.82 (quint, JCD ¼ 19 Hz, CHD2),
125.6 (s, p-Ph), 128.5 (s, m-Ph), 129.3 (s, o-Ph), 137.7 (s, ipso-PhCD3),
137.8 (s, ipso-PhCHD2). GCeMS (m/z): 94 ([PhCHD2]þ), 95
([PhCD3]þ).
2.6. X-ray structure analyses
The crystallographic data were measured on a Rigaku AFC-7R
Mercury-II with graphite-monochromated Mo-Ka (l ¼ 0.71069 Å).
A selected single crystal of 1 suitable for X-ray analysis was
mounted on the top of glass capillary by use of Paraton N oil under
argon. The reflection data were collected at 200 K under cold
●Masafumi Hirano, Yasutomo Arai, Nobuyuki Komine, and Sanshiro Komiya, Stoichiometric and
Catalytic Oxidative Coupling Reactions between Butadiene and Methyl Acrylate Promoted by
Ruthenium(0) Complex, Organometallics, 29, 5741-5743 (2010).
DOI: 10.1021/om100822n
●Masafumi Hirano, Yuki Hiroi, Nobuyuki Komine, and Sanshiro Komiya, Catalytic Tail-to-tail
Selective Dimerization of Methyl Methacrylate Promoted by Ruthenium(0) Complex,
Organometallics, 29, 3690-3693 (2010).
DOI: 10.1021/om100646q
●Masafumi Hirano, Sayaka Togashi, Muneaki Ito, Yuko Sakaguchi, Nobuyuki Komine, and Sanshiro
Komiya, Carbon-Hydrogen Bond Cleavage Reaction in 5-Coordinate
Bis(2,6-dimethylbenzenethiolato)ruthenium(II) Complexes, Organometallics, 29, 3146-3159 (2010).
DOI: 10.1021/om100249s
■ Papers before 2009 ●Shin-ichi Tanaka, Nobuyuki Komine, Masafumi Hirano and Sanshiro Komiya, Synthesis of
Heterodinuclear (Carbene)platinum (or palladium) Complex which Gives µ–Alkenyl Type
Complex by Deprotonation, Organometallics, 28, 5368-5381 (2009).
●Masafumi Hirano, Yumiko Sakate, Nobuyuki Komine, Sanshiro Komiya, and Martin A. Bennett,
Isolation of trans-2,5-Bis(methoxycarbonyl)ruthenacyclopentane by Oxidative Coupling of Methyl
Acrylate on Ruthenium(0) as an Active Intermediate for Tail-to-tail Selective Catalylic
Dimerization, Organometallics, 28, 4902-4905 (2009).
●Sanshiro Komiya, Sei Ezumi, Nobuyuki Komine and Masafumi Hirano, Visible Light Enhanced
Selective Reductive Elimination of Methylmanganese Complex from Heterodinuclear Dimethylphenyl(4,4´-di-tert-butyl-2,2´-bipyridine)platinum-pentacarbonylmanganese Complex,
Organometallics, 28, 3608-3610 (2009).
●Masafumi Hirano, Izirwan Bin Izhab, Naoki Kurata, Kaori Koizumi, Nobuyuki Komine and Sanshiro
Komiya, Reaction of an Oxaruthenacycle with DMAD.
Stoichiometric Transformations of
2,6-Xylenol to Allylic Phenols and Benzopyrans via sp3 C−H Bond Cleavage Reaction, Dalton
Transactions, 3270-3279 (2009)
●Masafumi Hirano, Toshinori Kuga, Mariko Kitamura, Susumu Kanaya, Nobuyuki Komine and
Sanshiro Komiya, Acid Promoted Hydrogen Migration in 2-Allylphenoxoruthenium(II) to Form an
η 3-Allyl Complex, Organometallics, 27, 3635-3638 (2008).
●Sanshiro Komiya, Akari Sako, Hirofumi Kosuge, Masafumi Hirano, and Nobuyuki Komine,
Mechanical Stirring in Water/Hexane Biphasic Catalyst Controls Regioselectivity of Pd-Catalyzed
Allylation Reaction, Chem. Lett., 37, 640-641 (2008).
●Nobuyuki Komine, Tomoko Ishiwata, Jun-ya Kasahara, Erino Matsumoto, Masafumi Hirano, and
Sanshiro Komiya, Synthesis and Organic Group Transfer of Organodiplatinum Complex Having a
1,2-Bis(diphenylphosphino)ethane Ligand, Can. J. Chem., 2009. 87, 176-182.
●Nobuyuki Komine, Takuma, Hirota, Masafumi Hirano, and Sanshiro Komiya, E-Selective Allyl
Transfer Reaction in µ−η 1:η 2-crotylplatinum-cobalt Complex, Organometallics, 27(9), 2145-2148
(2008).
●Nobuyuki Komine, Susumu Tsutsuminai, Masafumi Hirano, and Sanshiro Komiya, Synthesis and
Reactions of Heterodinuclear Organopalladium Complex Having an Unsymmetrical PN Ligand, J.
Organomet. Chem., 692(21), 4486-4494 (2007).
●Masafumi Hirano, Hiromi Sato, Naoki Kurata, Nobuyuki Komine, and Sanshiro Komiya,
Carbon-Oxygen and Carbon-Hydrogen Bond Cleavage Reaction of ortho-Substituted Phenols by
Ruthenium(II) Complex, Organometallics, 26(8), 2005-2016 (2007).
●Takao, Shibasaki, Nobuyuki Komine, Masafumi Hirano, and Sanshiro Komiya, Synthesis of Di-, Tri-,
Tetra- and Pentacyclic Arene Complexes of Ruthenium(II): [Ru(η 6-polycyclic
arene)(1-5-η 5-cyclooctadienyl)]PF6 and Their Reactions with NaBH4, J. Organomet. Chem., 692(12),
2385-2394 (2007).
●Shin-ichi Tanaka, Hideko Hoh, Yoshifumi Akahanea, Susumu Tsutsuminai, Nobuyuki Kominea,
Masafumi Hiranoa and Sanshiro Komiya,
Synthesis and Reactions of Heterodinuclear
Organopalladium–cobalt Complexes Acting as Copolymerization Catalyst for Aziridine and
Carbon Monoxide, J. Organomet. Chem. (2007) 692, 26-35.
●Nobuyuki Komine, Susumu Tsutsuminai, Hideko Hoh, Toshiyuki Yasuda, MasafumiHirano and
Sanshiro Komiya, Synthesis and Structures of Heterodinuclear Organoplatinum(or
-palladium)–molybdenum(or -tungsten) Complexes: Unexpected Structural Deformation of
Heterodinuclear Propionylplatinum–tungsten Complex Having 1,2-Bis(diphenylphosphino)ethane
Ligand, Inorg. Chim. Acta, (2006), 359, 2699-3708.
●Ayako Kuramoto, Kouhei Nakanishi, Tatsuya Kawabata, Nobuyuki Komine, Masafumi Hirano, and
Sanshiro Komiya, Palladium-assisted Regioselective Olefin Insertion into and –Hydrogen
Elimination of Hydrogen-molybdenum and –Tungsten Bonds.
Synthesis and Reactions of
Heterodinucelar Hydrido Complexes of Palladium and Platinum with Molybdenum and Tungsten,
Organometallics (2006), 25(2), 311-314.
●Takao Shibasaki, Nobuyuki Komine, Masafumi Hirano, and Sanshiro Komiya, Synthesis of Momo-,
Di and Trinuclear Ruthenium(0) Complexes Having a Triphenylene Ligand, Organometallics (2006),
25(2), 523-527.
●Nobuyuki Komine, Kaoru Ichikawa, Anna Mori, Masafumi Hirano, and Sanshiro Komiya, Enhanced
Reductive Elimination of Dialkylgold(III) Complexes in Water, Chemistry Letters, 34, (2005)
1704-1705.
●Masafumi Hirano, Yuko Sakaguchi, Toshiaki Yajima, Naoki Kurata, Nobuyuki Komine, and Sanshiro
Komiya. Stoichiometric and Catalytic sp3 C-H/D2 Exchange Reactions of ortho-Substituted
Benzenethiol and Phenols by a Ruthenium(II) Complex. Effect of a Chalcogen Anchor on the Bond
Cleavage Reaction,
Organometallics (2005) 24(20), 4799-4809.
●Kiyota, Sayori; Tamuki, Jun-ichi; Komine, Nobuyuki; Hirano, Masahumi; Komiya, Sanshiro.
Synthesis, Structure, and Fluxional Behavior of κ 1-O-Enolatoiron(II) Complexes Derived from
1,3-Dicarbonyl Compounds,
Chemistry Letters (2005), 34(4),
498-499.
●Komine, Nobuyuki; Sako, Akar; Hirahara, Shin-ya; Hirano, Masafumi; Komiya, Sanshiro.
Selective
allylation of arenethiols using water-soluble palladium complex catalyst in recyclable water/hexane
biphasic media.
Chemistry Letters
(2005),
34(2),
246-247.
●Kanaya, Susumu; Imai, Yuya; Komine, Nobuyuki; Hirano, Masafumi; Komiya, Sanshiro.
Dehydrogenative Formation of a (η4-Enone)ruthenium(0) Complex as a Key Intermediate in the
Catalytic Isomerization of Allylic Alcohol to Ketone.
Organometallics
(2005),
24(6),
1059-1061.
●Komine, Nobuyuki; Tanaka, Shin-ichi; Tsutsuminai, Susumu; Akahane, Yoshifumi; Hirano,
Masafumi; Komiya, Sanshiro.
Copolymerization of aziridines and carbon monoxide catalyzed by a
heterodinuclear organo palladium-cobalt complex.
858-859.
Chemistry Letters
(2004),
33(7),
●Tsutsuminai, Susumu; Komine, Nobuyuki; Hirano, Masafumi; Komiya, Sanshiro.
Enhanced C-C
Bond Formation of Heterodinuclear Methylplatinum-Molybdenum Complexes Having a
Hemilabile Ligand with Dialkyl Acetylenedicarboxylate.
Organometallics
(2004),
23(1),
44-53.
●Tsutsuminai, Susumu; Komine, Nobuyuki; Hirano, Masafumi; Komiya, Sanshiro.
Synthesis and
Reactions of Heterodinuclear Organoplatinum Complexes Having an Unsymmetrical PN Ligand.
Organometallics
(2003),
22(21),
4238-4247.
●Hirano, Masafumi; Onuki, Koji; Kimura, Yuichi; Komiya, Sanshiro.
Regioselective C-H or N-H
bond cleavage reactions of heterocyclic compounds by [Ru(1,5-COD)(1,3,5-COT)]/monodentate
phosphine.
Inorganica Chimica Acta
(2003),
352
160-170.
●Furuya, Masaki; Tsutsuminai, Susumu; Nagasawa, Hiroto; Komine, Nobuyuki; Hirano, Masafumi;
Komiya, Sanshiro.
Catalytic synthesis of thiobutyrolactones via CO insertion into the C-S bond of
thietanes in the presence of a heterodinuclear organoplatinum-cobalt complex.
Communications (Cambridge, United Kingdom)
(2003),
(16),
Chemical
2046-2047.
●Hirano, Masafumi; Asakawa, Rie; Nagata, Chifumi; Miyasaka, Takashi; Komine, Nobuyuki; Komiya,
Sanshiro.
Ligand Displacement Reaction of Ru(η4-1,5-COD)(η6-1,3,5-COT) with Lewis Bases.
Organometallics
(2003),
22(12),
2378-2386.
●Komiya, Sanshiro; Hirano, Masafumi.
Dalton Transactions
(2003),
(8),
Bond activation by low valent ruthenium complexes.
1439-1453.
●Komiya, Sanshiro; Ikuine, Miho; Komine, Nobuyuki; Hirano, Masafumi.
Synthesis and β-hydrogen
elimination of water-soluble dialkylplatinum(II) complexes in water.
Bulletin of the Chemical
Society of Japan
(2003),
76(1),
183-188.
●Hirano, Masafumi; Shibasaki, Takao; Komiya, Sanshiro; Bennett, Martin A.
Synthesis of and
Stereospecific Hydride Migration in Cationic (Tricyclic arene)(cyclooctadiene)ruthenium(II)
Complexes.
Organometallics
(2002),
21(26),
5738-5745.
●Komiva, Sanshiro; Ikuine, Miho; Komme, Nobuyuki; Hirano, Masafumi.
water-soluble diorganoplatinum(II) complexes.
Chemistry Letters
Synthesis and reactions of
(2002),
●Hirano, Masafumi; Osakada, Kohtaro; Nohira, Hiroyuki; Miyashita, Akira.
(1),
72-73.
Crystal and solution
structures of photochromic spirobenzothiopyran. First full characterization of the meta-stable
colored species.
Journal of Organic Chemistry
(2002),
67(2),
533-540.
●Kanaya, Susumu; Komine, Nobuyuki; Hirano, Masafumi; Komiya, Sanshiro.
Preferential bond
activation of sp3 C-H over sp2 C-H in α,β-unsaturated carboxylic acids by ruthenium complex.
Chemistry Letters
(2001),
(12),
1284-1285.
●Komiya, S.; Kuwahara, M.; Awazu, N.; Hirano, M.; Fukatani, J.
Preparation of highly dispersed
nano-scale platinum composite polymer using reactive organoplatinum complexes.
Materials Science Letters
(2001),
20(8),
Journal of
743-744.
●Fukuoka, Atsushi; Fukagawa, Sumiko; Hirano, Masafumi; Koga, Nobuaki; Komiya, Sanshiro.
Enhancement of CO Insertion into a Pd-C Bond in a Pd-Co Heterodinuclear Complex.
Organometallics
(2001),
20(10),
2065-2075.
●Komiya, S.; Yasuda, T.; Fukuoka, A.; Hirano, M..
Synthesis of hydridoplatinum-molybdenum (or
tungsten) heterodinuclear complexes by β-hydrogen elimination of (dppe)EtPt-MCp(CO)3.
Selective hydride transfer from Pt to Mo (or W).
(2000),
159(1),
Journal of Molecular Catalysis A: Chemical
63-70.
●Usui, Yoko; Noma, Junko; Hirano, Masafumi; Komiya, Sanshiro.
C-Si bond cleavage of
trihalomethyltrimethylsilane by alkoxo- and aryloxogold or -copper complexes.
Chimica Acta
(2000),
309(1-2),
Inorganica
151-154.
●Komine, Nobuyuki; Hoh, Hideko; Hirano, Masafumi; Komiya, Sanshiro.
Oxidative Addition of
Organocobalt(I) and -molybdenum(II) Complexes to Palladium(0) Complexes To Give
Heterodinuclear Organometallic Complexes.
Organometallics
(2000),
19(25),
5251-5253.
●Hirano, Masafumi; Kurata, Naoki; Komiya, Sanshiro.
Successive O-H and sp3 C-H bond
activation of ortho-substituted phenols by a ruthenium(0) complex.
Chemistry
(2000),
607(1-2),
Journal of Organometallic
18-26.
●Komiya, Sanshiro; Planas, Jose Giner; Onuki, Koji; Lu, Zhaobin; Hirano, Masafumi.
Versatile
Coordination Modes and Transformations of the Cyclooctatriene Ligand in Ru(C8H10)L3 (L =
Tertiary Phosphine).
Organometallics
(2000),
19(20),
4051-4059.
●Hirano, Masafumi; Kiyota, Sayori; Imoto, Masataka; Komiya, Sanshiro.
Michael addition of
N-bonded enolato ligands to acrylonitrile in iron and ruthenium complexes.
Communications (Cambridge)
(2000),
(17),
Chemical
1679-1680.
●Planas, Jose Giner; Marumo, Tsuyoshi; Ichikawa, Yoichi; Hirano, Masafumi; Komiya, Sanshiro.
Carbon-oxygen and carbon-sulfur bond activation of vinyl esters, ethers and sulfides by low valent
ruthenium complexes.
Dalton
(2000),
(15),
2613-2625.
●Komiya, Sanshiro; Muroi, Shin-ya; Furuya, Masaki; Hirano, Masafumi.
Regio- and Stereoselective
Insertion Reactions of Thiiranes into Pt-Mn (or Re) Bond in Organoplatinum-Manganese or
-Rhenium Heterodinuclear Complexes as Intermediates toward Desulfurization Reaction.
Journal of the American Chemical Society
(2000),
122(1),
170-171.
●Planas, J. G.; Marumo, T.; Ichikawa, Y.; Hirano, M.; Komiya, S.
C-O and C-S bond activation of
allyl esters, ethers, and sulfides by low valent ruthenium complexes.
Catalysis A: Chemical
(1999),
147(1-2),
137-154.
●Usui, Yoko; Noma, Junko; Hirano, Masafumi; Komiya, Sanshiro.
thiiranes by alkoxo- and aryloxo-gold(I) complexes.
Transactions: Inorganic Chemistry
(1999),
Journal of Molecular
(24),
Ring opening reactions of
Journal of the Chemical Society, Dalton
4397-4406.
●Fukuoka, A.; Sato, A.; Kodama, K.-y.; Hirano, M.; Komiya, S.
Synthesis of
organo(siloxo)platinum and -palladium complexes and preparation of supported nanoclusters by
facile ligand reduction.
Inorganica Chimica Acta
(1999),
294(2),
266-274.
●Morikita, Takashi; Hirano, Masafumi; Sasaki, Akito; Komiya, Sanshiro.
C-S, C-H, and N-H bond
cleavage of heterocycles by a zero-valent iron complex, Fe(N2)(depe)2 [depe =
1,2-bis(diethylphosphino)ethane].
Inorganica Chimica Acta
●Planas, Jose Giner; Hirano, Masafumi; Komiya, Sanshiro.
of Ru(η2-C2H3YPh)(cod)(depe) (Y = O, S).
(18),
291(1-2),
341-354.
Synthesis and ligand exchange control
Chemistry Letters
●Planas, Jose Giner; Hirano, Masafumi; Komiya, Sanshiro.
the C-S bond in 3-substituted thiophenes.
(1999),
(1999),
(9),
953-954.
Regioselective 1,2-insertion of Ru into
Chemical Communications (Cambridge)
(1999),
1793-1794.
●Hirano, Masafumi; Takenaka, Atsushi; Mizuho, Yuji; Hiraoka, Makiko; Komiya, Sanshiro.
Synthesis of N-bonded enolatoruthenium(II) by oxidative addition of alkyl cyanocarboxylate to a
ruthenium(0) complex.
(1999),
(18),
Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry
3209-3216.
●Doumeki, Reiko; Hatano, Masaharu; Kinoshita, Hiroo; Yamashita, Emi; Hirano, Masafumi; Fukuoka,
Atsushi; Komiya, Sanshiro.
Effect of Pt precursors on N2/N2O selectivity for selective reduction of
NO by hydrocarbon on supported Pt catalysts.
Chemistry Letters
(1999),
●Sato, Takehiro; Komine, Nobuyuki; Hirano, Masafumi; Komiya, Sanshiro.
(5),
515-516.
Selective isomerization
of 2-allylphenol to (Z)-2-propenylphenol catalyzed by Ru(COD)(COT)/PEt3.
(1999),
(6),
Chemistry Letters
441-442.
●Komiya, Sanshiro; Chigira, Tomoko; Suzuki, Toru; Hirano, Masafumi.
methacrylate catalyzed by hydridorhenium complexes.
Polymerization of alkyl
Chemistry Letters
(1999),
(4),
347-348.
●Fukuoka, Atsushi; Kosugi, Wataru; Morishita, Fumiaki; Hirano, Masafumi; Komiya, Sanshiro;
McCaffrey, Louise; Henderson, William.
Water-soluble iridium and rhodium complexes with
tris(hydroxymethyl)phosphine and their catalysis in biphasic hydrogenation and hydroformylation.
Chemical Communications (Cambridge)
(1999),
(6),
489-490.
●Nakahara, Naofumi; Hirano, Masafumi; Fukuoka, Atsushi; Komiya, Sanshiro.
Synthesis and
structure of thiolato bridged Pt-Ti heterobimetallic complexes with methyl group.
Organometallic Chemistry
(1999),
572(1),
Journal of
81-85.
●Hirano, Masafumi; Hirai, Miwa; Ito, Yuji; Tsurumaki, Tsutomu; Baba, Atsushi; Fukuoka, Atsushi;
Komiya, Sanshiro.
N-bonded enolatorhenium(I) complexes having dimethylphenylphosphine
ligands as active key intermediates in catalytic Knoevenagel and Michael reactions.
Organometallic Chemistry
(1998),
569(1-2),
Journal of
3-14.
●Alvarez, Salvador G.; Hasegawa, Sachi; Hirano, Masafumi; Komiya, Sanshiro.
Michael reactions
promoted by η1-O-enolatoruthenium(II) complexes derived from Ru(cod)(cot), diphosphine, and
dimethyl malonate.
Tetrahedron Letters
(1998),
39(29),
5209-5212.
●Fukuoka, Atsushi; Nagano, Takeyuki; Furuta, Shuichi; Yoshizawa, Michito; Hirano, Masafumi;
Komiya, Sanshiro.
complexes.
Tail-to-tail dimerization of acrylonitrile catalyzed by low-valent ruthenium
Bulletin of the Chemical Society of Japan
●Kubo, Hiroaki; Hirano, Masafumi; Komiya, Sanshiro.
(1998),
71(6),
1409-1415.
Synthesis, structure and reactivity of an
(η 6-naphthalene)iron(0) complex having a 1,2-bis(dicyclohexylphosphino)ethane ligand.
of Organometallic Chemistry
(1998),
556(1-2),
Journal
89-95.
●Planas, Jose Giner; Hirano, Masafumi; Komiya, Sanshiro.
C-S bond cleavage of allyl thioethers by
zerovalent Ru complexes.
(2),
Chemistry Letters
(1998),
123-124
●Hirano, Masafumi; Kurata, Naoki; Marumo, Tsuyoshi; Komiya, Sanshiro.
Successive O-C/O-H and
sp3 C-H Bond Activation of ortho Substituents in Allyl Phenyl Ethers and Phenols by a
Ruthenium(0) Complex.
Organometallics
(1998),
17(4),
501-503.
●Yasuda, Toshiyuki; Fukuoka, Atsushi; Hirano, Masafumi; Komiya, Sanshiro.
Pt-Mo heterodinuclear hydride complexes promoted by alkynes.
(1),
29-30.
Hydrogen transfer in
Chemistry Letters
(1998),
●Hirano, Masafumi; Akita, Masatoshi; Morikita, Takashi; Kubo, Hiroaki; Fukuoka, Atsushi; Komiya,
Sanshiro.
Synthesis, structure and reactions of a dinitrogen complex of iron(0), [Fe(N2)(depe)2]
(depe = Et2PCH2CH2PEt2).
Chemistry
(1997),
(19),
Journal of the Chemical Society, Dalton Transactions: Inorganic
3453-3458.
●Usui, Yoko; Hirano, Masafumi; Fukuoka, Atsushi; Komiya, Sanshiro.
Hydrogen abstraction from
transition metal hydrides by gold alkoxides giving gold-containing heterodinuclear complexes.
Chemistry Letters
(1997),
(10),
981-982.
●Hirano, Masafumi; Akita, Masatoshi; Tani, Kazuo; Kumagai, Kuninori; Kasuga, Noriko C.; Fukuoka,
Atsushi; Komiya, Sanshiro.
Activation of Coordinated Carbon Dioxide in Fe(CO2)(depe)2 by
Group 14 Electrophiles.
Organometallics
(1997),
16(19),
4206-4213.
●Fukuoka, Atsushi; Fukagawa, Sumiko; Hirano, Masafumi; Komiya, Sanshiro.
Insertion of CO into
a CH3-Pd bond in a heterodinuclear complex (dppe)MePd-Co(CO)4. Preferential insertion of
coordinated CO on a cobalt moiety.
Chemistry Letters
(1997),
(4),
377-378.
●Fukuoka, Atsushi; Sugiura, Takeshi; Yasuda, Toshiyuki; Taguchi, Tomokazu; Hirano, Masafumi;
Komiya, Sanshiro.
Enhancement of β-hydrogen elimination reaction on platinum-containing
heterodinuclear complexes.
Chemistry Letters
(1997),
(4),
329-330.
●Hirano, Masafumi; Marumo, Tsuyoshi; Miyasaka, Takashi; Fukuoka, Atsushi; Komiya, Sanshiro.
Unexpected ligand displacement of Ru(cod) with trimethylphosphine to give
fac-Ru(6-η1:1-3-η3-C8H10)(PMe3)3.
Chemistry Letters
(1997),
(4),
297-298.
●Komiya, Sanshiro; Sone, Takuo; Usui, Yoko; Hirano, Masafumi; Fukuoka, Atsushi.
Condensation
reactions of benzaldehyde catalyzed by gold alkoxides.
(1996),
Gold Bulletin (London)
29(4),
131-136.
●Fukuoka, Atsushi; Minami, Yutaka; Nakajima, Nobumasa; Hirano, Masafumi; Komiya, Sanshiro.
Synthesis and reactivity of organoplatinum-rhenium heterobimetallic complexes having sulfur
ligands.
Journal of Molecular Catalysis A: Chemical
(1996),
107(1-3),
323-328.
●Murahashi, Shun-Ichi; Naota, Takeshi; Taki, Hiroshi; Mizuno, Masahiko; Takaya, Hikaru; Komiya,
Sanshiro; Mizuho, Yuji; Oyasato, Naohiko; Hiraoka, Makiko; Hirano, Masafumi; Fukuoka; Atsushi.
Ruthenium-catalyzed aldol and Michael reactions of nitriles. Carbon-carbon bond formation by
α-C-H activation of nitriles.
Journal of the American Chemical Society
(1995),
117(50),
12436-51.
●Fukuoka, Atsushi; Gotoh, Naotaka; Kobayashi, Norikazu; Hirano, Masafumi; Komiya, Sanshiro.
Homogeneous bimetallic catalysts for production of carboxylic acids from carbon dioxide,
hydrogen, and organic iodides.
Chemistry Letters
(1995),
(7),
567-8.
●Fukuoka, Atsushi; Sato, Akihiro; Mizuho, Yuji; Hirano, Masafumi; Komiya, Sanshiro.
Synthesis
and structure of novel organo(siloxo)platinum complexes. Facile reduction by dihydrogen.
Chemistry Letters
(1994),
(9),
1641-4.
●Komiya, Sanshiro; Kabasawa, Takashi; Yamashita, Koji; Hirano, Masafumi; Fukuoka, Atsushi.
C-O
bond cleavage and oxidative addition of an allyl carboxylate to a ruthenium(0) complex. Isolation of
(π-allyl)(trifluoroacetato)tris(triethylphosphine)ruthenium(II).
Chemistry
(1994),
471(1-2),
Journal of Organometallic
C6-C7.
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