Ring-closing metathesis within chromium-coordination sphere: Facile access to phosphine-chelate (π-arene)chromium complexes

Article abstract of DOI:10.1016/j.jorganchem.2011.05.006

A variety of phosphine-chelate (π-arene)chromium complexes were prepared in good to excellent yields by the ring-closing metathesis reaction of [η⁶-(ω-alkenyl)benzene][(ω-alkenyl)phosphine] chromium(0) dicarbonyl complexes catalyzed by the Grub

Full text of DOI:10.1016/j.jorganchem.2011.05.006

Journal of Organometallic Chemistry 696 (2011) 3987e3991
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Ring-closing metathesis within chromium-coordination sphere:
Facile access to phosphine-chelate (p
-arene)chromium complexesq
,
b
a
b
a
Masamichi Ogasawara a , Wei-Yi Wu , Sachie Arae , Tomotaka Morita , Susumu Watanabe ,
**
*
Tamotsu Takahashi a , Ken Kamikawa
,
b,
***
a Catalysis Research Center and Graduate School of Life Science, Hokkaido University, Kita-ku, Sapporo 001-0021, Japan
b Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai Osaka 599-8531, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
A variety of phosphine-chelate (
by the ring-closing metathesis reaction of [
p
-arene)chromium complexes were prepared in good to excellent yields
6-(
-alkenyl)benzene][( -alkenyl)phosphine]chromium(0)
dicarbonyl complexes catalyzed by the Grubbs’ rutheniumecarbene complexes.
Ó 2011 Elsevier B.V. All rights reserved.
Received 9 April 2011
Received in revised form
4 May 2011
h
u
u
Accepted 6 May 2011
Keywords:
(p-Arene)chromium complex
Alkenylphosphine
Ring-closing metathesis
Ruthenium-carbene complex
1. Introduction
blocks based on planar-chirality [6]. In this article, we wish to
report preparation of the phosphine-chelate (
6-arene)chromium
complexes by the Ru-catalyzed ring-closing metathesis. This type
of bridged (
6-arene)chromium species is relatively rare and all the
precedented examples are prepared by ligation of a preformed
phosphine-tethered arene to a chromium center [7].
h
Since the discovery of well-defined metathesis catalysts, olefin
metathesis has been widely recognized as a versatile and powerful
tool in organic chemistry and material science [1]. Due to the
excellent functional group tolerance of the Schrock’s Mo- [2] and
the Grubbs’ Ru-catalysts [3], they have been utilized in modulation
of a wide range of organic compounds. In the last decade, organ-
ometallic compounds have emerged as a novel class of substrates in
olefin metathesis, and the Mo- and the Ru-catalysts show good
versatility in the transformation of the organometallic substrates as
well [4]. The metathesis reactions of the organometallics have
provided the unique ways to interesting structures which are
otherwise difficult to access [4,5]. The majority of the earlier works
in this field is on the ferrocene platforms, which can partly be
attributed to their chemical robustness, and the metathesis studies
on other organometallics are still rather limited.
h
The RCM studies on the arene-chromium compounds were
previously reported by Sarkar and coworkers [8]. In their system, the
two alkenyl side chains are arranged on the arene ring. The reaction
cites are remote from the chromium-coordination spheres and the
(h
6-arene)chromium moieties exist outside of the newly formed
rings (the exo-cyclization mode; Scheme 1). In other words, the exo-
mode cyclization is a process converting the single ligand by the
RCM reaction. On the other hand, the RCM reaction of (h
6-arene)
chromium species described here proceeds within the chromium-
coordination spheres connecting the two coordinating ligands (an
h
6-arene and a phosphine), which leads to the formation of the
In organometallic chemistry, (
h
6-arene)chromium complexes
chromium-containing ring systems (the endo-cyclization mode).
are one of the most useful compounds because not only of their
unique reactivity but also of their usefulness as chiral building
2. Results and discussion
q
2.1. Preparation of (h6
alkenylphosphine) complexes 1
-u-alkenylbenzene)Cr(CO)2(u-
Dedicated to Professor Kenneth G. Caulton on the occasion of his 70th birthday.
* Corresponding author. Tel.: þ81 11 706 9154; fax: þ81 11 706 9150.
** Corresponding author. Tel.: þ81 11 706 9149; fax: þ81 11 706 9150.
*** Corresponding author. Tel.: þ81 72 254 9721; fax: þ81 72 254 9931.
E-mail addresses: ogasawar@cat.hokudai.ac.jp (M. Ogasawara), tamotsu@cat.
hokudai.ac.jp (T. Takahashi), kamikawa@c.s.osakafu-u.ac.jp (K. Kamikawa).
A
series of h6
miumcomplexes were prepared bya photo-induced ligand exchange
-u-alkenylbenzene/u-alkenylphosphineechro-
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.05.006

3988
M. Ogasawara et al. / Journal of Organometallic Chemistry 696 (2011) 3987e3991
Table 1
Ring-closing metathesis of preparing phosphine-chelate (
h
6-arene)chromium(0)
complexes.a
Scheme 1. Two reaction modes of RCM on chromium-arene platforms.
reaction as illustrated in Scheme 2 [9]. Photoirradiation of a pre-
formed (h6
-alkenylbenzene)chromium(0) tricarbonyl complex
in benzene with a high-pressure mercury lamp in the presence of
an excess (1.5 equiv. to Cr) appropriate -alkenylphosphine
entry
Substrate 1
Catalyst
(mol %)
Solvent
Time
(h)
Temp
Yield of 2
(ꢀC)
(%)b
-u
1
2
3
4
5
6
7
1a
1b
1c
1c
1d
1d
1d
A (10)
A (10)
A (10)
B (10)
A (10)
B (10)
C (10)
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
C6H6
6
6
25
25
25
25
25
50
80
93 (2a)
82 (2b)
60 (2c)
71 (2c)
0c
u
18
18
18
18
18
(u-alkenyl ¼ vinyl or allyl) induces a ligand exchange between CO
and the phosphine to give a dicarbonyl(alkenylphosphine)chromium
complex in moderate to good yields (58e80%). The complexes are red
to yellow poorly crystalline solids. They are slightly air-sensitive but
easily purified by silica gel chromatography under nitrogen.
0
0d
a
The reaction was carried out in the given solvent under argon with initial
concentration of 1 at 0.1 mol/L in the presence of the indicated catalyst (10 mol %).
b
Isolated yield by silica gel chromatography.
The unreacted substrate 1d was recovered in >80%.
The major product was 3d in 68%.
c
2.2. Preparation of phosphine-chelate (
complexes by ruthenium-catalyzed ring-closing metathesis
h
6-arene)chromium(0)
d
It was found that the
h
6-styrene/allyldiphenylphosphine
complex 1a was an excellent substrate for the endo-mode ring-
closing metathesis. A reaction of 1a with the 1st generation
Grubbs’ catalyst (A; 10 mol %) in dichloromethane at 25 ꢀC was
complete within 6 h and the NMR analysis of the reaction mixture
showed nearly quantitative formation of the desired phosphine-
chelate complex 2a. The pure RCM product 2a was isolated in
93% yield as a yellow crystalline solid by silica gel chromatography
(Table 1, entry 1). The Cr complex 1b, which is with a diisopropyl-
phosphino moiety in place of the PPh2 unit, is equally reactive as 1a
under the identical reaction conditions (entry 2). The isolated yield
of 2b (82%) is slightly lower than that of 2a, that can be attributed to
the lower stability of 2b toward oxidation due to the more electron-
donating phosphine (i.e., the higher electron density at the chro-
mium center). The RCM reaction of the substrate 1c, which is with
be rationalized as depicted in Scheme 3. Isomerization of the
substrate 1c, which was likely promoted by a Ru-hydride species
derived by decomposition of the Grubbs catalysts [10], gives the
(h
6-propenylbenzene)chromium complex 3c, and following RCM of
3c afforded 2a with elimination of propene [11].
On the other hand, the RCM reaction of the
h
6-allylbenzene/
vinyldiphenylphosphine complex 1d, which was expected to
produce the C3-bridged phosphine-chelate (
h
6-arene)chromium
complex 2d, did not afford the cyclized product under the condi-
tions examined. With the ruthenium catalyst A (10 mol %) at 25 ꢀC,
the unreacted substrate was recovered in >80% yield (entry 5).
Under the more severe conditions, i. e. with the catalyst B at 50 ꢀC,
consumption of 1d was observed in a certain extent, but the desired
chelate complex 2d was not found in the reaction mixture (entry 6).
The Mo catalyst C, which is known to be powerful for sterically
congested substrates, was not effective for the reaction of 1d either.
More than 95% of 1d was consumed at 80 ꢀC during 18 h in the
presence of C (10 mol %), however, the main product (68%) from the
reaction was the isomerized complex 3d and no RCM product was
detected (entry 7). It seems that the diphenylphosphino group
adjacent to the vinyl moiety exerts a steric effect which suppresses
the formation of 2d.
an h
6-allylbenzene, was tardier and the product 2c was obtained in
60% yield (entry 3). The use of the 2nd generation Grubbs’ catalyst
(B) was found to be more effective for the reaction of 1c, and the
yield of 2c was improved to 71% (entry 4). Note that the reactions of
1c (entries 3 and 4) are not so clean as those of 1a and 1b, and
several uncharacterized byproducts were detected in the 1H and 31
P
NMR spectra of the reaction mixtures. Some of the byproducts can
be ascribed to results of intermolecular cross-metathesis. Among
the byproducts from the reaction of 1c, about 5% of 2a was
observed. The formation of the “shortened” chelate complex 2a can
In general, ring sizes and substitution patterns are two of the
most important factors for success of RCM. The results shown above
imply that an
combination for the high-yield preparation of the phosphine-
h
6-vinylarene and an allylphosphine are the best
chelate (
p
-arene)chromium species by endo-cyclization RCM.
Scheme 2. Preparation of h6
complexes 1.
-u-alkenylbenzene/u-alkenylphosphineechromium
Scheme 3. Plausible pathway from 1c to 2a.

M. Ogasawara et al. / Journal of Organometallic Chemistry 696 (2011) 3987e3991
3989
A distinctive color change was observed during the ring-closing
metathesis of 1a and 1b. The color of the
6-styrene complexes (1a
and 1b) is bright red, while that of the
6-allylbenzene complexes
(1c and 1d) is light yellow. The darker colors in 1a and 1b can be
explained by the conjugation of the vinyl groups and the
6-arene
h
h
h
moieties in these two complexes. On the other hand, all of the RCM
products 2a-c are light yellow in color as 1c and 1d. In 2a and 2b,
the
h a,u-alkenylene moieties are not
6-arene and the bridging
conjugating anymore due to their non-coplanar orientation (see
their crystal structures; vide infra), which cancels the red-shift
detected in 1a and 1b. In accordance with this, the complex 3d,
which has an h b-methylstyrene) ligand, is bright red as 1a and
6-(
1b.
The non-chelate Cr-complexes 1a-d and 3d show the 31P NMR
82.4 to 84.9, which is the typical range for
this type of complexes. On the other hand, the 31P NMR signals of 2a
resonances between
d
d
and 2b are detected at
d 104.6 and d 119.8, respectively. This
unusual lower field shift of the 31P-NMR resonances would be
ascribed to the distorted geometries of the phosphorus atoms in 2a
and 2c in response to the ring strain due to the shorter C3-chain
between the h
6-phenyl and diphenylphosphino groups. Indeed, the
Fig. 2. ORTEP drawing of 2c with 30% thermal ellipsoids. All hydrogen atoms are
omitted for clarity. Selected bond lengths (Å) and angles (deg): Cr(1)eP(1) ¼ 2.2871(8),
distortion can be seen in the crystal structure of 2a (see the next
section). The C4-bridged complex 2c, of which three-dimensional
structure is close to the ideal piano-stool geometry, does not
Cr(1)eC(5)
¼
2.224(2), P(1)eC(1)
¼
1.847(2), C(1)eC(2)
¼
1.501(4), C(2)e
6-arene) ¼ 1.693;
C(3) ¼ 1.310(5), C(3)eC(4) ¼ 1.490(5), C(4)-C(5) ¼ 1.491(4), Cr(1)-(
h
P(1)eCr(1)eC(5) 95.08(7), Cr(1)eP(1)eC(1) 115.61(8), Cr(1)eP(1)e
¼
¼
show the lower field shift in its 31P NMR spectrum (
d 75.8).
C(13) ¼ 115.29(8), Cr(1)eP(1)eC(19) ¼ 120.34(8), Cr(1)eC(5)eC(4) ¼ 131.2(2).
2.3. X-ray crystal structures of 2a and 2c
Thus, the geometry around the P(1) atom in 2a is far from the ideal
tetrahedral orientation. In contrast, the three Cr(1)-P(1)-carbon
angles in 2c are in the range 115.29(8)-120.34(8)ꢀ. Likewise, due
to the skewed chelate ring in 2a, the C(4)-Cr(1)-P(1) angle in 2a
(84.6(1)ꢀ) is considerably smaller than the C(5)-Cr(1)-P(1) angle in
2c (95.08(7)ꢀ). The CreP distances are 2.271(1) Å in 2a and
2.2871(8) Å in 2c respectively, which are approximately 5% shorter
Single crystals of 2a and 2c suitable for X-ray crystallography
were grown from ethyl acetate/hexane at low temperature. Their
ORTEP drawings are shown in Figs. 1,2, along with selected bond
lengths and angles (see the Supporting Information for details). The
structure of 2a clearly displays the distorted conformation of the
molecule as suggested by the 31P NMR spectrum. The Cr(1)-P(1)e
C(1) angle is 110.4(1)ꢀ, which is much smaller than the angles of
Cr(1)-P(1)eC(12) (116.8(1)ꢀ) and Cr(1)-P(1)eC(18) (121.6(1)ꢀ).
than the CreP distance in an analogous non-chelate complex (h6
-
benzene)Cr(CO)2(PPh2CH2Ph) (2.4015(14) Å) [12]. Other bond
lengths and angles in 2a and 2c are within the normal range.
2.4. Origin of high reactivity of 1a and 1b in RCM
As described in the section 2.3, the RCM product 2a contains the
distortion originated in the shorter chelate chain. Comparison
between the two structures suggests that the strain energy in 2a is
probably larger than that in 2c. Corollary of these observations is
that relative thermodynamic stability of the RCM products cannot
account for the higher reactivity of 1a and 1b than 1c in the RCM
reaction. Most likely, the RCM reactions of 1a-c are under kinetic
control. With a shorter alkenyl substituent (vinyl group) on the h6
-
arene in 1a and 1b, the probability of meeting the two olefinic
termini becomes higher leading to the higher yields of 2a and 2b
than 2c. Alternatively, the higher yields of 2a/2b could be explained
by the greater reactivity of the
h
6-styrene moieties in 1a and 1b
than the
h
6-allylbenzene in 1c [13,14].
3. Conclusions
In conclusion, we have successfully achieved efficient endo-cycli-
zation within the coordination sphere of the (
6-arene)chromium
h
Fig. 1. ORTEP drawing of 2a with 30% thermal ellipsoids. All hydrogen atoms are
omitted for clarity. Selected bond lengths (Å) and angles (deg): Cr(1)e
P(1) ¼ 2.271(1), Cr(1)eC(4) ¼ 2.201(4), P(1)eC(1) ¼ 1.842(3), C(1)eC(2) ¼ 1.509(6),
complexes by the RCM reaction. The reactivity of the substrates is
strongly affected by length of the olefinic tethers, and choice of
suitable alkenyl substituents is important for higher yields of the RCM
products. Future outlook: explorations of the asymmetric synthesis of
C(2)eC(3) ¼ 1.303(6), C(3)eC(4) ¼ 1.492(5), Cr(1)-(
h
6-arene) ¼ 1.689; P(1)eCr(1)e
C(4) ¼ 84.6(1), Cr(1)eP(1)eC(1) ¼ 110.4(1), Cr(1)eP(1)eC(12) ¼ 116.8(2), Cr(1)e
P(1)eC(18) ¼ 121.6(1), Cr(1)eC(4)eC(3) ¼ 130.3(3).
planar-chiral (h
6-arene)chromium complexes are in progress.

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M. Ogasawara et al. / Journal of Organometallic Chemistry 696 (2011) 3987e3991
4. Experimental section
NMR (C6D6):
d
39.4 (s), 40.6 (d, JPC ¼ 22.6 Hz), 88.2 (s), 88.6 (s), 91.2
(s), 105.5 (d, JPC ¼ 0.9 Hz), 116.9 (s), 118.8 (d, JPC ¼ 10.0 Hz), 128.1 (d,
J ¼ 8.1 Hz), 129.0 (d, JPC ¼ 2.1 Hz), 131.6 (d, JPC ¼ 5.0 Hz), 132.6 (d,
JPC ¼ 9.7 Hz),136.6 (s),140.6 (d, JPC ¼ 28.3 Hz), 240.8 (d, JPC ¼ 20.6 Hz).
4.1. General
All anaerobic and/or moisture sensitive manipulations were
carried out with standard Schlenk techniques under predried
nitrogen or with glovebox techniques under prepurified argon. 1H
NMR (at 400 MHz) and 13C NMR (at 101 MHz) chemical shifts are
reported in ppm downfield of internal tetramethylsilane. 31P NMR
(at 162 MHz) chemical shifts are externally referenced to 85%
H3PO4. Tetrahydrofuran and benzene were distilled from
benzophenone-ketyl under nitrogen prior to use. Dichloromethane
was distilled from CaH2 under nitrogen prior to use. The chromium
31P{1H} NMR (C6D6): 83.5 (s). IR (CHCl3) 1879, 1825, 1092 cmꢁ1
d .
Anal. Calcd for C26H25CrO2P: C, 69.02; H, 5.57. Found: C, 69.04; H,
5.62. EI-HRMS Calcd for C26H25CrO2P: 452.0997. Found: 452.0995.
4.2.4. (h
6-Allylbenzene)(diphenylvinylphosphine)chromium(0)
dicarbonyl (1d)
Yield: 74%. 1H NMR (C6D6):
d
2.93 (d, J ¼ 6.8 Hz, 2H), 4.10e4.14
(m, 1H), 4.22e4.23 (m, 2H), 4.37e4.41 (m, 2H), 4.88e4.94 (m, 2H),
5.44 (td, 17.8 and 1.7 Hz, 1H), 5.56 (ddd, J ¼ 35.7, 11.8, and 1.7 Hz,
1H), 5.79 (ddt, J ¼ 17.8, 9.6, and 6.8 Hz, 1H), 6.54 (ddd, J ¼ 17.8, 17.2,
and 11.8 Hz,1H), 6.99e7.10 (m, 6H), 7.53e7.58 (m, 4H). 13C{1H} NMR
tricarbonyl complexes
(h
6-arene)Cr(CO)3 [15], (PCy3)2Cl2
-
Ru(¼CHPh) [3b], (H2IMes)(PCy3)Cl2Ru(¼CHPh) [16], and
Mo(¼CHCMe2Ph)(¼NC6H3-2,6-iPr2)(OC(CF3)2Me)2 [1a,17] were
prepared according to the reported methods. All the other chem-
icals were obtained from commercial sources.
(C6D6):
d
39.4 (s), 88.1 (s), 88.5 (s), 91.2 (s), 105.5 (d, JPC ¼ 0.9 Hz),
117.0 (s), 127.2 (d, JPC ¼ 4.4 Hz), 128.3 (d, JPC ¼ 8.9 Hz), 129.2 (d,
JPC ¼ 2.1 Hz), 132.7 (d, JPC ¼ 10.4 Hz), 136.5 (s), 138.9 (d,
JPC ¼ 33.1 Hz), 140.1 (d, JPC ¼ 34.3 Hz), 240.4 (d, JPC ¼ 21.0 Hz). 31P
4.2. Preparation of nonbridged (
h
6-arene)Cr(CO)2(phosphine) 1
{1H} NMR (C6D6): 84.3 (s). IR (KBr) 1877,1820 cmꢁ1. Anal. Calcd for
d
C25H23CrO2P: C, 68.49; H, 5.29. Found: C, 68.77; H, 5.45. EI-HRMS
Calcd for C25H23CrO2P: 438.0841. Found: 438.0835.
A chromium tricarbonyl complex (1 mmol) and an appropriate
alkenylphosphine (1.5 mmol) were dissolved in benzene (10 mL)
under an argon atmosphere. The solution was irradiated with
mercury lamp and stirred for 7 h at room temperature. The
resulting red color solution was filtrate and concentrated under
reduced pressure. The crude product was purified by silica gel
chromatography to give the target compound in 58e80% yield. The
characterization data of the complexes are given below.
4.3. General procedure for the ring-closing metathesis of 1
A solution of the chromium complex 1 (0.50 mmol) and the
Grubbs’ catalyst (50 mmol; 10 mol%) in CH2Cl2 (5 mL) was stirred at
25 ꢀC for 6e18 h under a nitrogen atmosphere. The resulting solu-
tion was concentrated under reduced pressure. The residue was
purified by silica gel chromatography to give the cyclized product.
4.2.1. (h
6-Vinylbenzene)(allyldiphenylphosphine)chromium(0)
dicarbonyl (1a)
4.3.1. [h
6-(3-Diphenylphosphinopropenyl)benzene-P]chromium(0)
Yield: 68%. 1H NMR (C6D6):
d
3.06e3.11 (m, 2H), 4.20e4.29 (m,
dicarbonyl (2a)
3H), 4.46e4.49 (m, 2H), 4.70e4.76 (m, 1H), 4.82e4.86 (m, 1H), 4.93
(dd, J ¼ 10.7 and 0.6 Hz, 1H), 5.23 (dd, J ¼ 17.4 and 0.6 Hz, 1H),
5.66e5.77 (m, 1H), 5.96 (dd, J ¼ 17.4 and 10.7 Hz, 1H), 7.00e7.11 (m,
1H NMR (C6D6):
4.01e4.04 (m, 2H), 4.32e4.36 (m, 1H), 4.71e4.75 (m, 2H), 5.39 (ddt,
J ¼ 13.1, 11.0, and 5.8 Hz, 1H), 6.03 (ddt, J ¼ 11.0, 3.0, and 1.7 Hz, 1H),
6.99e7.04 (m, 2H), 7.06e7.11 (m, 4H), 7.47e7.52 (m, 4H). 13C{1H}
d
2.56 (ddd, J ¼ 8.9, 5.8, and 1.7 Hz, 2H),
6H), 7.45e7.50 (m, 4H).13C{1H} NMR (C6D6):
d
40.4 (d, JPC ¼ 22.7 Hz),
87.4 (s), 89.2 (s), 90.0 (s), 99.4 (s), 113.3 (s), 118.9 (d, JPC ¼ 10.0 Hz),
128.1 (d, JPC ¼ 8.3 Hz), 129.1 (d, JPC ¼ 2.0 Hz), 131.4 (d, JPC ¼ 5.0 Hz),
132.6 (d, JPC ¼ 10.0 Hz), 135.8 (s), 140.4 (d, JPC ¼ 28.4 Hz), 240.6 (d,
NMR (C6D6):
d
30.8 (d, JPC ¼ 14.1 Hz), 80.8 (d, JPC ¼ 0.9 Hz), 85.6 (s),
91.0 (d, JPC ¼ 1.1 Hz), 100.4 (d, JPC ¼ 3.0 Hz), 128.2 (d, JPC ¼ 9.1 Hz),
128.6 (d, JPC ¼ 12.6 Hz), 128.8 (s), 129.1 (d, JPC ¼ 2.1 Hz), 132.2 (d,
JPC ¼ 20.7 Hz). 31P{1H} NMR (C6D6):
d
82.4 (s). IR (KBr) 1654,
JPC ¼ 10.0 Hz), 140.4 (d, JPC ¼ 35.0 Hz), 238.5, (d, JPC ¼ 18.9 Hz). 31
P
1542 cmꢁ1. Anal. Calcd for C25H23CrO2P: C, 68.49; H, 5.29. Found: C,
68.47; H, 5.44. EI-HRMS Calcd for C25H23CrO2P: 438.0841. Found:
438.0842.
{1H} NMR (C6D6): 104.6 (s). IR (CHCl3) 1890, 1831 cmꢁ1. Anal.
d
Calcd for C23H19CrO2P: C, 67.32; H, 4.67. Found: C, 67.02; H, 4.87. EI-
HRMS Calcd for C23H19CrO2P: 410.0528. Found: 410.0530.
4.2.2. (
h
6-Vinylbenzene)(allyldiisopropylphosphine)chromium(0)
4.3.2. [
chromium(0) dicarbonyl (2b)
1H NMR (C6D6):
h
6-1-(3-Diisopropylphosphino-2-propenyl)benzene-P]
dicarbonyl (1b)
Yield: 80%. 1H NMR (C6D6):
d
0.94 (dd, J ¼ 13.9 and 7.2 Hz, 6H),
d
0.88 (dd, J ¼ 12.5 and 7.0 Hz, 6H), 1.00 (dd,
1.00 (dd, J ¼ 12.6 and 7.2 Hz, 6H), 1.69e1.78 (m, 2H), 2.48 (t,
J ¼ 7.4 Hz, 2H), 4.44e4.51 (m, 3H), 4.61e4.63 (m, 2H), 4.91e5.00 (m,
3H), 5.33 (d, J ¼ 17.6 Hz, 1H), 5.77e5.89 (m, 1H), 6.12, (dd, J ¼ 17.6
J ¼ 14.5 and 7.2 Hz, 6H), 1.62e1.66 (m, 2H), 1.80e1.92 (m, 2H),
4.12e4.14 (m, 2H), 4.40e4.47 (m, 3H), 5.46e5.55 (m,1H), 5.98e6.01
(m, 1H). 13C{1H} NMR (C6D6):
d
17.2 (d, JPC ¼ 0.6 Hz), 18.4 (d,
and 10.8 Hz, 1H). 13C{1H} NMR (C6D6):
d
18.7 (d, JPC ¼ 3.0 Hz), 19.0
JPC ¼ 3.0 Hz), 22.0 (d, JPC ¼ 6.8 Hz), 28.9 (d, JPC ¼ 19.8 Hz), 81.6 (s),
88.1 (d, JPC ¼ 1.5 Hz), 88.8 (s), 96.5 (d, JPC ¼ 2.4 Hz), 129.2 (s), 241.5
(d, JPC ¼ 17.3 Hz), 241.0 (d, JPC ¼ 18.0 Hz). 31P{1H} NMR (C6D6):
(s), 28.9 (d, JPC ¼ 14.8 Hz), 34.3 (d, JPC ¼ 16.9 Hz), 85.1 (s), 87.1 (s),
87.4 (s), 98.0 (s), 113.0 (s), 117.2 (d, JPC ¼ 7.4 Hz), 134.0 (d,
JPC ¼ 6.5 Hz), 136.3 (s), 241.5 (d, JPC ¼ 19.8 Hz). 31P{1H} NMR (C6D6):
d
119.8 (s). IR (CHCl3) 1870, 1815 cmꢁ1. Anal. Calcd for C17H23CrO2P:
d
84.9 (s). IR (KBr) 1880, 1826 cmꢁ1. Anal. Calcd for C21H31CrO2P: C,
C, 59.64; H, 6.77. Found: C, 59.30; H, 6.81. EI-HRMS Calcd for
C19H27CrO2P: 342.0841. Found: 342.0839.
61.61; H, 7.35. Found: C, 61.71; H, 7.42. EI-HRMS Calcd for
C19H27CrO2P: 370.1154. Found: 370.1149.
4.3.3. [
chromium(0) dicarbonyl (2c)
1H NMR (C6D6):
h
6-(4-Diphenylphosphinobut-2-enyl)benzene-P]
4.2.3. (h
6-Allylbenzene)(allyldiphenylphosphine)chromium(0)
dicarbonyl (1c)
d
2.84 (d, J ¼ 7.6 Hz, 2H), 3.07 (dd, J ¼ 9.4 and
Yield: 58%. 1H NMR (C6D6):
d
2.90 (dt, J ¼ 6.7 and 1.3 Hz, 2H), 3.11
7.3 Hz, 1H), 4.46e4.54 (m, 3H), 4.60e4.62 (m, 2H), 5.21e5.35 (m,
(t, J ¼ 7.9 Hz, 2H), 4.05e4.09 (m, 1H), 4.15e4.16 (m, 2H), 4.32e4.36
(m, 2H), 4.70e4.77 (m, 1H), 4.83e4.89 (m, 2H), 4.91e4.93 (m, 1H),
5.68e5.81 (m, 2H), 7.00e7.10 (m, 6H), 7.47e7.52 (m, 4H). 13C{1H}
2H), 7.01e7.06 (m, 2H), 7.10e7.14 (m, 4H), 7.45e7.50 (m, 4H). 13C
{1H} NMR (C6D6):
d
31.3 (s), 32.8 (d, JPC ¼ 11.6 Hz), 85.4 (s), 85.8
(d, JPC ¼ 0.7 Hz), 90.4 (s), 97.0 (s), 126.5 (d, JPC ¼ 8.6 Hz), 128.1 (d,

M. Ogasawara et al. / Journal of Organometallic Chemistry 696 (2011) 3987e3991
3991
(b) R.R. Schrock Chapter 1.3, in: R.H. Grubbs (Ed.), Handbook of Metathesis,
vol. 1, Wiley-VCH, Weinheim, 2003, p. 8.
[3] (a) S.T. Nguyen, L.K. Johnson, R.H. Grubbs, J.W. Ziller, J. Am. Chem. Soc. 114
(1992) 3974;
JPC ¼ 8.6 Hz), 128.9 (d, JPC ¼ 2.0 Hz), 129.1 (d, JPC ¼ 3.7 Hz), 132.1 (d,
JPC ¼ 10.0 Hz), 142.0 (d, JPC ¼ 34.0 Hz), 239.6 (d, JPC ¼ 20.0 Hz). 31
P
{1H} NMR (C6D6):
d
75.8 (s). IR (CHCl3) 1883,1824 cmꢁ1. Anal. Calcd
(b) P. Schwab, R.H. Grubbs, J.W. Ziller, J. Am. Chem. Soc. 118 (1996) 100;
(c) M. Scholl, S. Ding, C.W. Lee, R.H. Grubbs, Org. Lett. 1 (1999) 953;
(d) S.T. Nguyen, T.M. Trnka Chapter 1.6, in: R.H. Grubbs (Ed.), Handbook of
Metathesis, vol. 1, Wiley-VCH, Weinheim, 2003, p. 61.
[4] E.B. Bauer, J.A. Gladysz Chapter 2.11, in: R.H. Grubbs (Ed.), Handbook of
Metathesis, vol. 2, Wiley-VCH, Weinheim, 2003, p. 403.
[5] Examples of Enantio-/Diastereo-Selective Preparation of Chiral Metallocenes:
(a) A.J. Locke, C. Jones, C.J. Richards, J. Organomet. Chem. 637e639 (2001) 669;
(b) M. Ogasawara, T. Nagano, T. Hayashi, J. Am. Chem. Soc 124 (2002) 9068,
J. Am. Chem. Soc. 124 (2002) 12626;
for C24H21CrO2P: C, 67.92; H, 4.99. Found: C, 67.75; H, 5.10. EI-HRMS
Calcd for C24H21CrO2P: 424.0684. Found: 424.0678.
4.3.4. (
chromium(0) dicarbonyl (3d)
1H NMR (C6D6):
h
6-1-Propenylbenzene)(diphenylvinylphosphine)
d
1.55 (d, J ¼ 5.1 Hz, 3H), 4.28e4.31 (m, 1H),
4.36e4.39 (m, 2H), 4.51e4.53 (m, 2H), 5.40e5.75 (m, 4H), 6.55 (ddd,
J ¼ 18.1, 17.4, and 11.9 Hz, 1H), 6.99e7.10 (m, 6H), 7.54e7.58 (m, 4H).
(c) M. Ogasawara, S. Watanabe, L. Fan, K. Nakajima, T. Takahashi, Organo-
metallics 25 (2006) 5201;
(d) M. Ogasawara, S. Watanabe, K. Nakajima, T. Takahashi, Pure Appl. Chem.
80 (2008) 1109;
(e) M. Ogasawara, S. Watanabe, K. Nakajima, T. Takahashi, J. Am. Chem. Soc.
132 (2010) 2136.
13C{1H} NMR (C6D6):
d 18.2 (s), 86.8 (s), 89.1 (s), 89.5 (s), 101.3 (d,
JPC ¼ 0.9 Hz), 125.9 (s), 127.1 (d, JPC ¼ 4.4 Hz), 128.2 (d, JPC ¼ 8.8 Hz),
129.1 (d, JPC ¼ 2.0 Hz), 129.6 (s), 132.9 (d, JPC ¼ 10.6 Hz), 138.9 (d,
JPC ¼ 32.9 Hz), 140.0 (d, JPC ¼ 33.8 Hz), 240.5 (d, JPC ¼ 20.9 Hz). 31
P
{1H} NMR (C6D6): 84.0 (s). IR (KBr) 1883,1831 cmꢁ1. EI-HRMS Calcd
d
[6] (a) L.-X. Dai, T. Tu, S.-L. You, W.-P. Deng, X.-L. Hou, Acc. Chem. Res. 36 (2003)
659;
for C25H23CrO2P: 438.0841. Found: 438.0841.
(b) A. Togni, N. Bieler, U. Burckhardt, C. Knöllner, G. Pioda, R. Schneider,
A. Schnyder, Pure Appl. Chem. 71 (1999) 1531;
(c) M.F. Semmelhack, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 12, Elsevier Science, Oxford,
1995, p. 979;
(d) M.F. Semmelhack, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 12, Elsevier Science, Oxford,
1995, p. 1017;
(e) S.G. Davies, T.D. McCarthy, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 12, Elsevier Science, Oxford,
1995, p. 1039;
4.4. X-ray crystallography of 2a
CCDC number 820585. Crystal data: empirical formula,
C23H19O2PCr, M ¼ 410.35, orange needles, monoclinic, space group,
P21/C, a ¼ 12.636(3)Å, b ¼ 11.302(3)Å, c ¼ 14.075(3)Å, V ¼ 1953.6(8)
Å3, Z ¼ 4, Dc ¼ 1.395 g/cm3, F(000) ¼ 848.0,
m
(Mo K
a
) ¼ 0.682 mm-1,
T ¼ 296 K, R1 ¼ 0.0547 (I > 2
s
(I)), wR2 ¼ 0.1865 (I > 2 (I)), S ¼ 1.018,
s
(f) H.-G. Schmalz, S. Siegel, in: C. Bolm, M. Beller (Eds.), Transition Metals for
Fine Chemicals and Organic Synthesis, vol. 1, VCH, Weinheim, 1998, p. 550;
(g) K.P. Kaliappan, E.P. Kündig, Chem. Rev. 100 (2000) 2917;
number of collected data
¼
18502, number of refined
parameters ¼ 245. Data collection was carried out using the RIGAKU
RAXIS RAPID, and SHELXL97 programs were used for the structure
solution and refinement.
(h) E.P. Kündig (Ed.), Transition Metal Arene
p-Complexes in Organic
Synthesis and Catalysis, Topics in Organometallic Chemistry, vol. 7, Springer,
Berlin, 2004, pp. 21e30.
[7] (a) A.N. Nesmeyanov, V.V. Krivykh, P.V. Petrovskii, M.I. Rybinskaya, Dokl.
Akad. Nauk SSSR 231 (1976) 110;
4.5. X-ray crystallography of 2c
(b) A.N. Nesmeyanov, V.V. Krivykh, M.I. Rybinskaya, Dokl. Akad. Nauk SSSR
239 (1978) 1363;
CCDC number 820584. Crystal data: empirical formula,
C24H21O2PCr, M ¼ 424.38, orange needles, monoclinic, space group,
(c) A.N. Nesmeyanov, Y.T. Struchkov, V.G. Andrianov, V.V. Krivykh,
M.I. Rybinskaya, J. Organomet. Chem. 164 (1979) 51;
(d) A.N. Nesmeyanov, V.V. Krivykh, G.A. Panosyan, P.V. Petrovskii,
M.I. Rybinskaya, J. Organomet. Chem. 164 (1979) 159;
(e) A.N. Nesmeyanov, V.V. Krivykh, M.I. Rybinskaya, J. Organomet. Chem. 164
(1979) 167;
P21/c,
a
¼
12.704(6)Å,
b
¼
11.357(4)Å,
c
¼
14.368(5)Å,
V ¼ 2023.9(13)Å3, Z ¼ 4, Dc ¼ 1.393 g/cm3, F(000) ¼ 880.0,
m(Mo
Ka
) ¼ 0.661 mm-1, T ¼ 296 K, R1 ¼ 0.0404 (I > 2
(I)), wR2 ¼ 0.1104
s
(I > 2
s
(I)), S ¼ 1.018, number of collected data ¼ 19345, number of
(f) A.N. Nesmeyanov, Y.T. Struchkov, V.G. Andrianov, V.V. Krivykh,
M.I. Rybinskaya, J. Organomet. Chem. 166 (1979) 211;
(g) W.R. Jackson, I.D. Rae, M.G. Wong, Aust. J. Chem. 37 (1984) 1563;
(h) W.R. Jackson, I.D. Rae, M.G. Wong, Aust. J. Chem. 39 (1986) 303.
[8] B.C. Maity, V.M. Swamy, A. Sarkar, Tetrahedron Lett. 42 (2001) 4373.
[9] W. Strohmeier, H. Hellmann, Chem. Ber. 63 (1963) 2859.
[10] (a) S.E. Lehman Jr., J.E. Schwendeman, P.M. O’Donnell, K.B. Wagener, Inorg.
Chim. Acta 345 (2003) 190;
refined parameters ¼ 253. Data collection was carried out using the
RIGAKU RAXIS RAPID, and SHELXL97 programs were used for the
structure solution and refinement.
Acknowledgments
(b) B. Schmidt, Eur. J. Org. Chem. (2004) 1865.
[11] The formation of propene could not be detected due to the low yield (5%) of
2a.
[12] J. Geicke, I.-P. Lorenz, K. Polborn, Inorg. Chim. Acta 272 (1998) 101.
[13] D.R. Lane, C.M. Beavers, M.M. Olmstead, N.E. Schore, Organometallics 28
(2009) 6789.
[14] Although this Possibility could not be Ruled Out, We Prefer the Explanation as
the Kinetic Control, because the yields of [4]ferrocenophanes (from 1,10-dia-
llylferrocenes) are generally higher than those of [5]ferrocenophanes (from 1-
allyl-10-butenylferrocenes) in the analogous RCM reactions of producing the
bridged ferrocenes. See: (a) M. Ogasawara, S. Watanabe, K. Nakajima,
T. Takahashi, Organometallics 27 (2008) 6565;
This work was supported by the Cooperative Research Program
from the Catalysis Research Center, Hokkaido University (Grant
#10A0002) and a Grant-in-Aid for Scientific Research on Innovative
Areas from MEXT, Japan (to MO and KK).
Appendix. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jorganchem.2011.05.006.
(b) Ref. 5e.
[15] (a) M.D. Rausch, G.A. Moser, E.J. Zaiko, A.L. Lipman, J. Organomet. Chem. 23
(1970) 185;
References
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