DOI: 10.1002/cctc.

201100185
Ligand-Consuming Formation of Rhodium-Hydride Species from
[Rh(OH)(cod)]2 Without any Additional Hydride Sources for Catalytic Olefin
Isomerizations and Cyclobutene Synthesis
Ken Motokura, Kohei Nakayama, Akimitsu Miyaji, and Toshihide Baba*[a]

General methods for the formation of metal hydrides (M H) re-

quire an additional hydride source (Scheme 1 a). To realize the
formation of a metal hydride without additives, we investigat-

Scheme 1. a) Metal-hydride formation with a hydride source, and b) ligand-

consuming generation of a metal-hydride.

ed the ligand-consuming formation of the metal hydride, as
shown in Scheme 1 b. If hydride abstraction from a ligand
occurs at the metal center, the structure of the ligand molecule
coordinating to the metal should changes. The distorted
ligand can then be expected to be easily eliminated from the
metal center. This ligand-consuming methodology should
enable the formation of not only metal hydrides, but also gen-
erate a coordinatively unsaturated environment at the metal
center, which would be expected to be catalytically active.
The cyclooctadienerhodium hydroxide dimer {[Rh(OH)-
(cod)]2} (COD = 1,5-cyclooctadiene) is a well known homogene-
ous catalyst. Although various organic transformations using
[Rh(OH)(cod)]2 have been reported,[1,2] its reactivity is limited to
the transmetallation between the Rh OH and R X (X = B, Si, H
(activated), etc.) groups or the Rh alkoxide formation from the
R OH group. Discovery of novel reaction pathways and cataly-
ses for [Rh(OH)(cod)]2 have thus received considerable
attention.
Mimoun and coworkers reported a Wacker-type oxidation of
C=C bonds via a Rh OH intermediate, affording ketones and
Rh H.[3,4] The stoichiometric oxidation of the COD-ligand of
[(N3-ligand)-RhI(cod)]+ with H2O2 was also reported.[3,5] These re-
sults encouraged us to investigate the ligand-consuming for-
mation of Rh H species from [Rh(OH)(cod)]2 through oxidation
of its COD ligand by the OH group (Scheme 2). If this reaction
[a] Dr. K. Motokura, K. Nakayama, Dr. A. Miyaji, Prof. T. Baba
Department of Environmental Chemistry and Engineering
Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku
Yokohama, 226-8502 (Japan)
E-mail: tbaba@chemenv.titech.ac.jp
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201100185.
Scheme 2. Generation of Rh H species from [Rh(OH)(cod)]2.
proceeds, oxidized COD [cyclooctenone (1 a) and cyclooctadie-
nol (1 b)] and a coordinatively unsaturated Rh H species
should form.[6] Herein, we report a novel phenomenon for the
generation of Rh H species from [Rh(OH)(cod)]2 for catalytic
reactions.
cis/trans-Isomerization of Z-stilbene is a well-known metal-
hydride catalyzed reaction. This isomerization was examined
using several rhodium complexes (Table 1).[7] [Rh(OH)(cod)]2
showed a high catalytic performance, however, the reaction
barely proceeded using [RhCl(cod)]2 and [Rh(cod)2]BF4. Follow-
ing the reaction using [Rh(OH)(cod)]2, 1 a and 1 b were detect-
ed in the reaction mixture. The total amount of 1 a, 1 b, and
their isomers was 12 mmol.[8] Migration of terminal olefins
using [Rh(OH)(cod)]2 was also examined (Table 2). Allylben-
zenes with electron-donating groups were effectively trans-
Table 1. cis/trans-Isomerization of Z-Stilbene.[a]
Catalyst Conversion [%] Yield [%]
[Rh(OH)(cod)]2 98 88
[RhCl(cod)]2 5 2
[Rh(cod)2]BF4 7 3
none 10 2
[a] Reaction conditions: Z-stilbene (1.0 mmol), catalyst (Rh: 82 mmol), 1,4-
dioxane (2 mL), 100 8C, Ar, 24 h.

ChemCatChem 2011, 3, 1419 1421  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1419
 Table 2. Double Bond Migration of Terminal Olefins.[a]
Entry Substrate Conversion [%] Yield [%]
1 R=H 88 85
2 R = p-CH3-Ph 92 89
3 R = p-OMe-Ph 93 92
4 R= > 99 99
5 R = SiMe3 78 78
[a] Reaction conditions: olefin (1.0 mmol), catalyst (rhodium: 82 mmol),
1,4-dioxane (2 mL), 100 8C, Ar, 1 h.
ferred to conjugated products with approximately 90 % E-se-
lectivity, which was accompanied by the formation of 1 a and
1 b.[9,10]
To confirm the formation of Rh H species under the catalyt-
ic reaction conditions, hydride transfer reactions using deuter-
ated styrenes were performed. The reaction between
[D8]styrene (> 98 atom % D) and allylbenzene afforded deuter-
ated 1-propenylbenzene (Scheme 3). The amount of deuterium
in the styrene double bond decreased to approximately 63
83 %. Incorporation of deuterium into the terminal methyl
group of 1-propenylbenzene indicates that the insertion of the
allylbenzene double bond into the Rh H (Rh D) species oc-
curred during olefin migration. In addition, the treatment of a-
deuterated styrene (> 98 atom % D) with [Rh(OH)(cod)]2 in-
duced migration of deuterium (Scheme 4). These results clearly
indicate in situ formation of a Rh H species. To confirm the hy-
dride source, migration of p-methyl(allyl)benzene was exam-
ined in 1,4-[D8]dioxane. Incorporation of deuterium into the
migration product did not occur (Scheme 5). This result indi-
cates that the dioxane solvent did not act as a hydride source.
Consequently, the olefin isomerizations were catalyzed by the
Rh H species generated in situ from Rh OH and its COD
ligand.
The high field 1H NMR spectrum of a solution of [Rh(OH)-
(cod)]2 in 1,4-[D8]dioxane is shown in Figure 1. The resonance
centered at d = 1.20 ppm with a 103Rh H coupling of 44.1 Hz
indicates the formation of a Rh H species.[11] This signal ap-
pears at a lower field compared to other reported metal-hy-
dride complexes (d = 5 to 40 ppm) with electron-donating
ligands such as PPh3.[11,12] This result suggests a coordinatively
unsaturated environment of the in situ generated Rh H spe-
cies. The integration of this signal is considerably smaller (
Scheme 3. Reaction between [D8]styrene and allylbenzene.
1420 www.chemcatchem.org  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
E:Z Scheme 4. Migration of deuterium induced by treatment of a-deuterated
styrene with [Rh(OH)(cod)]2.
93:7
88:12
87:13
93:7
92:7
Scheme 5. Migration of p-methyl(allyl)benzene in 1,4-[D8]dioxane.
Figure 1. High field 1H NMR spectrum of [Rh(OH)(cod)]2 in 1,4-[D8]dioxane.
Rh H: (d = 1.20 ppm, doublet, J103Rh H = 44.1 Hz).
10 3) than that of the [Rh(OH)(cod)]2 signal appearing at d =
1.53.5 ppm (see the Supporting Information). Almost all of
the [Rh(OH)(cod)]2 complex is stable, and the amount of the
Rh H species is significantly lower than that of [Rh(OH)(cod)]2
under 1H NMR analysis conditions. Conversely, after isomeriza-
tion of Z-stilbene, 12 mmol of oxidized COD (1) forms from
41 mmol of [Rh(OH)(cod)]2. These results indicate that approxi-
mately 15 % of [Rh(OH)(cod)]2 is converted into the Rh H spe-
cies during the catalytic reaction.
Recently, MizorokiHeck-type coupling reactions between al-
kynes and electron-deficient olefins were reported for Pd H
and Ru H catalysts.[13] To extend the catalytic application of
the in situ generated Rh H species, the coupling reaction of
diphenylacetylene and methyl acrylate (2) was examined using
[Rh(OH)(cod)]2. Contrary to ex-
pectation, an 81 % yield of 1,2-
diphenyl-3-methoxycarbonylcy-
clobutene (3) was obtained as
the main product, accompanied
by a 12 % yield of the Mizoroki
Heck-type eneyne coupling
products (4), as shown in
Table 3, entry 1. These products
ChemCatChem 2011, 3, 1419 1421
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2 [RhCl(cod)]2 OMe 25 2 <1 trace
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4 none OMe <1 trace trace trace
11261.
5 [Rh(OH)(cod)]2 O nBu > 99 83 7 2
[6] Closed-shell allylic C H activation of COD and a radical chain electron
6 [Rh(OH)(cod)]2 NH tBu > 99 65 17 10
transfer oxidation of COD involving disproportionation of small
[a] Reaction conditions: diphenylacetylene (1.0 mmol), 2 (0.33 mmol), cat- amounts of rhodium(II) intermediates have been reported, see: a) M.
alyst (rhodium: 82 mmol), 1,4-dioxane (2 mL), 80 8C, Ar, 24 h. Yields and Martn, E. Sola, O. Torres, P. Plou, L. A. Oro, Organometallics 2003, 22,
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were barely detected when using [RhCl(cod)]2 and [Rh- alyst precursor; however, the formation of oxidized COD and the rhodi-
um hydride species from above mentioned pathways cannot be com-
(cod)2]BF4 rather than [Rh(OH)(cod)]2. Other electron-deficient pletely ruled out.
olefins, such as acrylamide derivatives, are also suitable for the [7] D. Gauthier, A. T. Lindhardt, E. P. K. Olsen, J. Overgaard, T. Skydstrup, J.
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This is the first report of a cyclobutene synthesis from al- [8] The ketone/alcohol ratio was 1.8/1.0.
[9] To exclude the possibility of a base-catalyzed migration mechanism
kynes and electron-deficient olefins.[14] The mechanism for the (Ref. 9), the reaction of p-methyl(allyl)benzene in the presence of D2O
cyclobutene formation has not yet been clarified. Two plausi- was performed. MS and 1H NMR analysis revealed no incorporation of
ble pathways include a metallacyclopentene intermediate or deuterium into the migration product (see the Supporting Information).
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