Rhodium versus iridium catalysts in the controlled tandem hydroformylation-isomerization of functionalized unsaturated fatty substrates

Article abstract of DOI:10.1002/cctc.201402783

The hydroformylation of 10-undecenitrile (1) and related unsaturated fatty substrates (H₂C=CH(CH₂)₇CH₂R; R=CO₂Me, CH₂Br, CHO) has been studied with rhodium, iridium, ruthenium, and palladium biphephos catalysts. The reactions proceeded effectively with all four systems, with high selectivities for the linear aldehyde (ratio of linear/branched aldehydes=99:1). The biphephos-bis[chloro(cyclooctadiene)iridium] system showed a non-optimized hydroformylation turnover frequency (TOF_HF) of 770h^-1 that was only approximately 5times lower than that of the rhodium-based system (TOF_HF=3320h^-1); the palladium and ruthenium biphephos systems were less active (TOF_HF=210 and 310h^-1, respectively). Upon recycling, remarkable productivities were achieved in both cases (TON≈58-000mol(1/1-int)-mol(Ir)^-1 and 250-000mol(1/1-int)-mol(Rh)^-1, in which int=internal olefin). Competitive isomerization of terminal to internal olefins occurred with these catalysts. Iridium biphephos systems allowed slightly better control of the distribution of the internal isomers than the rhodium biphephos catalyst, with higher ratios of 9-/8-undecenitrile (1-int). Place your bets now: Iridium-biphephos catalysts are highly effective in the controlled tandem isomerization-hydroformylation of 10-undecenitrile and related functionalized unsaturated fatty substrates.

Full text of DOI:10.1002/cctc.201402783

DOI: 10.1002/cctc.201402783
Full Papers
Rhodium versus Iridium Catalysts in the Controlled
Tandem Hydroformylation–Isomerization of Functionalized
Unsaturated Fatty Substrates
Jꢀrꢀmy Ternel,[a] Jean-Luc Couturier,[b] Jean-Luc Dubois,[c] and Jean-FranÅois Carpentier*[a]
The hydroformylation of 10-undecenitrile (1) and related unsat-
urated fatty substrates (H2C=CH(CH2)7CH2R; R=CO2Me, CH2Br,
CHO) has been studied with rhodium, iridium, ruthenium, and
palladium biphephos catalysts. The reactions proceeded effec-
tively with all four systems, with high selectivities for the linear
aldehyde (ratio of linear/branched aldehydes=99:1). The bi-
phephos-bis[chloro(cyclooctadiene)iridium] system showed
a non-optimized hydroformylation turnover frequency (TOFHF)
of 770 hÀ1 that was only approximately 5 times lower than that
of the rhodium-based system (TOFHF =3320 hÀ1); the palladium
and ruthenium biphephos systems were less active (TOFHF =
210 and 310 hÀ1, respectively). Upon recycling, remarkable pro-
ductivities were achieved in both cases (TONꢀ58000 mol(1/1-
int)mol(Ir)À1 and 250000 mol(1/1-int)mol(Rh)À1, in which int=
internal olefin). Competitive isomerization of terminal to inter-
nal olefins occurred with these catalysts. Iridium biphephos
systems allowed slightly better control of the distribution of
the internal isomers than the rhodium biphephos catalyst, with
higher ratios of 9-/8-undecenitrile (1-int).
Introduction
Hydroformylation is the most widely applied homogeneously
catalyzed process in industry; more than 10 million tons of al-
dehyde products are produced each year and converted
mainly into plasticizers, solvents, and detergent alcohols.[1] The
reaction, discovered by Roelen in 1938,[2] was initially per-
formed with cobalt catalysts, which dominated academic and
industrial hydroformylation chemistry for several decades.
Nowadays, the majority of studies and some important indus-
trial processes rely on rhodium-based catalysts, which are
more active and allow a higher selectivity for the production
of linear aldehydes with negligible quantities of alkanes.[3]
However, the price of rhodium—a precious metal in high
demand and limited supply—is quite high and extremely vola-
tile.[4] There is thus a strong interest for catalysts based on
more readily available metals to achieve hydroformylation.[5]
Yet, in contrast to the extensive studies performed on cobalt
and rhodium systems, other metals have received less atten-
tion, most likely because of their generally lower activity[5,6]
(Rh@Co>Ir, Ru>Os>Pt>Pd@Fe>Ni, as established for un-
modified metal carbonyl complexes)[7] and chemoselectivity in
hydroformylation. Catalysts based on iridium, a metal cheaper
than rhodium but also with a relatively volatile price,[4] have
long remained underdeveloped in hydroformylation due to
their tendency to promote side-hydrogenation under hydrofor-
mylation conditions.[8] Nonetheless, recent reinvestigations
have demonstrated a good potential of this metal.[5,9] For in-
stance, Beller and co-workers described the use of a triphenyl-
phosphine-modified iridium catalyst that was only 8 times
slower than its rhodium homologue in the hydroformylation of
various olefins, with selectivities for linear aldehydes in the
range 68–97%.[9a] The potential of ruthenium catalysts in hy-
droformylation has been also investigated.[5,10] The groups of
Drent and Beller have reported palladium phosphine catalysts
modified with strong acids as co-catalysts that can afford alde-
hydes (sometimes in mixtures with alcohols) with modest ac-
tivity but up to 95% regioselectivity for the linear aldehydes.[11]
From economic and environmental point of views, one of
the most challenging goals in current hydroformylation re-
search is the selective conversion of internal olefins to linear al-
dehydes. The main obstacle is the isomerization process. This
does not represent a huge problem for shorter alkenes but, for
longer chain alkenes, internal isomers are present and/or
formed in significant amounts and can eventually give access
to a series of undesired branched aldehydes. To date, a few
catalyst systems enable the selective conversion of internal al-
kenes towards terminal aldehydes.[12] Two strategies can be
used. The first consists of dual hydroformylation–isomerization
catalytic systems similar to those reported by the groups of
Beller[13] and Nozaki,[14] relying on the use of a simple rhodium
catalyst for hydroformylation and a ruthenium catalyst for
[a] Dr. J. Ternel, Prof. Dr. J.-F. Carpentier
Organometallics, Materials and Catalysis
UMR 6226 Institut des Sciences Chimiques de Rennes
CNRS-University of Rennes 1
F-35042 Rennes (France)
Fax: (+33)0223-236-939
E-mail: jean-francois.carpentier@univ-rennes1.fr
[b] Dr. J.-L. Couturier
Arkema France, CRRA, BP
63, Rue Henri Moissan, F-69493 Pierre Bꢀnite (France)
[c] Dr. J.-L. Dubois
Arkema France
420 Rue d’Estienne d’Orves, F-92705 Colombes (France)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201402783.
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isomerization, albeit with rela-
tively large loadings of the latter
metal to achieve the isomeriza-
tion–hydroformylation of 2-
butene. Also, Reek et al. em-
ployed a combination of palladi-
um triphenylphosphine and
supramolecular rhodium bis-
phosphite catalysis for achieving
the synthesis of a-methyl- Scheme 1. Hydroformylation and isomerization products arising from 1.
branched aldehydes from termi-
nal olefins.[15] The second—and
likely most efficient strategy—remains the use of a single cata-
lyst comprising a group VIII element and specific phosphorus-
based ligands.[12] Hence, effective isomerization–hydroformyla-
tion of 2-olefins, such as 2-octene and 2-hexene, to linear alde-
hydes has been achieved with rhodium catalysts associated
with bulky phosphite ligands of Union Carbide Corp. [ratio of
linear/branched aldehydes (l/b)=19 for 2-hexene][3b] and
DuPont–DSM (l/b=35 for 2-hexene),[16] Van Leuween’s Xant-
phos derivatives (l/b=9.5 for 2-octene),[3e-g] Bçrner’s acylphos-
phite ligands (l/b=2.2 for a mixture of octene isomers),[17] sub-
stituted Naphos-type ligands designed by Beller (l/b=10.1 for
2-octene),[18] and Zhang’s tetraphosphorous ligands (l/b=362
for 2-hexene and 267 for 2-octene) (Figure 1).[19] Also, efficient
Rh-based catalytic systems have been reported for the isomeri-
zation–hydroformylation of functional C3ÀC5 olefins such as
pentenenitriles.[20]
toward biosourced polyamide-12.[21] The reaction, which was
also extended to related functionalized unsaturated fatty sub-
strates, was performed at very high substrate/rhodium ratios
(20000–100000) and allowed access to the desired linear alde-
hydes with high chemo- and regioselectivities up to 93 and
99%, respectively. However, these fatty C11 compounds could
give access to significant amounts of undesired isomerization
products [e.g., 1-int (int=internal olefin) in the case of 1]
under the hydroformylation conditions, which eventually
plagued both conversions and selectivities for the desired
linear aldehydes (Scheme 1).
Herein, we report new results on the isomerization–hydro-
formylation of 1 and related functionalized unsaturated fatty
substrates. Our objectives are two-fold: 1) to achieve hydrofor-
mylation with high regioselectivity, while controlling the distri-
bution of the internal isomers formed; indeed, cis/trans-9-iso-
mers produced from a 10-olefin can be valuable compounds
for special applications, such as in the fragrance industry; and
2) to investigate alternative catalysts based on metals other
than rhodium. Thus, the tandem isomerization–hydroformyla-
tion of a series of functionalized
In a previous study, we reported the use of an efficient (ace-
tylacetonato)dicarbonylrhodium-biphephos catalyst system for
the tandem isomerization–hydroformylation of the unsaturated
fatty nitrile 10-undecenitrile (1, Scheme 1), as a potential route
unsaturated fatty substrates has
been performed with homoge-
neous rhodium, iridium, rutheni-
um, and palladium diphosphane
catalysts. The conditions for ach-
ieving high selectivities and pro-
ductivities, including an effective
recycling of the hydroformyla-
tion catalyst, are described.
Results and Discussion
Single-batch hydroformylation
of 1
Different Ir catalyst precursors
were first evaluated in combina-
tion with biphephos under the
conditions optimized previously
in the Rh-biphephos-catalyzed
hydroformylation of 1,[21] chosen
here as a model substrate. The
results, summarized in Table 1
(see also Tables S1–S4), indicate
Figure 1. Typical phosphorus-based ligands associated to Rh for effective isomerization–hydroformylation of inter-
nal olefins.[12]
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These performances were only
slightly affected after decreasing
the catalyst loading to [1]0/
[metal] up to 50000 (entries 1,2
vs. 3,4). In contrast, the nature
of the solvent (entries 2 vs. 7–9)
and catalyst precursor (entries 2,
11, and 14) appeared more im-
portant; in fact, significantly
higher amounts of the hydroge-
nation product undecanenitrile
(4)—the only side-product ob-
served besides those from the
isomerization of 1 (see the dis-
cussion below)—were observed
with [Ir(acac)(cod)] as precursor,
in contrast to [IrCl(cod)]2 and
[IrCpMe(cod)] as precursors, for
reactions performed in toluene.
Use of [Ir(acac)(cod)] as precur-
sor gave better performance in
acetonitrile (entries 11 vs. 13).
Table 1. Hydroformylation–isomerization of 1/1-int promoted by Rh- and Ir-biphephos systems.[a]
Entry Precursor
[M]
[1]0/[M] Solvent
1[b] 1-int[b] 9-/8- 2+3[b] 2/3 4[b] Conv. 1[c] HF[d]
[%] [%]
undec [%]
[%] [%]
[%]
1[e]
2
3
4
5[f]
6[f]
7
8
9
10
11
12
13
14
[Rh(acac)(CO)2] 20000 toluene
[IrCl(cod)]2 20000 toluene
[Rh(acac)(CO)2] 50000 toluene
[IrCl(cod)]2 50000 toluene
[Rh(acac)(CO)2] 20000 toluene
0
0
0
16
22
21
22
7
81/19 79
86/14 73
89/11 75
92/8 65
98/2 46
99/1
99/1
99/1
99/1
97/3
98/2
99/1
99/1
99/1
99/1
5
5
4
5
2
2
5
5
4
4
100
100
100
92
83
77
79
75
92
69
73
74
80
77
70
60
78
78
76
75
80
83
80
8
45
82
0
53
14
[IrCl(cod)]2
[IrCl(cod)]2
[IrCl(cod)]2
[IrCl(cod)]2
[IrCl(cod)]2
20000 toluene
20000 tetrahydrofuran
20000 N-methyl-2-pyrrolidone 25 18
20000 acetonitrile
50000 acetonitrile
7
26
95/5
9
88/12 69
95/5 52
92/8 75
93/7 69
92/8 64
96/4 30
88/12 74
90/10 62
88/12 76
93/7 73
84/16 75
94/6 72
92/8 72
100
74
1
5
3
20
22
21
99
95
97
53
[Ir(acac)(cod)] 20000 toluene
[Ir(acac)(cod)] 50000 toluene
[Ir(acac)(cod)] 20000 acetonitrile
99/1 12
99/1 12
45 13
22
16 18
0
99/1
99/1
99/1
99/1
99/1
99/1
99/1
4
4
5
4
4
4
5
100
83
100
98
[IrCpMe(cod)]
20000 toluene
20000 toluene
15[g] Pd(acac)2
16[h] [RuCl2(PPh3)3] 20000 toluene
18[i]
19[i]
20[i]
0
2
1
8
4
19
21
20
16
19
[Rh(acac)(CO)2] 20000 bulk
[Ir(acac)(cod)] 20000 bulk
[RuCl2(PPh3)3] 20000 bulk
99
92
96
[a] Reaction conditions unless otherwise stated: 1/1-int (95:5, 5.0 mmol), [biphephos]0/[M]=20, solvent (5 mL),
P=20 bar CO/H2 (1:1), T=1208C, t=5 h (Rh), 20 h (Ir), 72 h (Ru, Pd). [b] Distribution [mol%] of remaining 1 and
internal alkenes 1-int, aldehydes 2 and 3, and hydrogenation product 4, as determined by NMR and GLC analy-
ses. [c] Conversion of 1. [d] Selectivity for hydroformylation products (2+3) vs. isomerization and hydrogena-
tion. [e] Results from Ref. [21]. [f] With Xantphos as ligand. [g] t=72 h. [h] t=48 h. [i] A minimal amount
(0.5 mL) of toluene (Rh and Ru) or acetonitrile (Ir) was used to introduce the catalyst precursors.
Both the Ir- and Rh-biphephos
systems catalyzed the parallel
isomerization of 1 and, at total
conversion of the terminal olefin,
induced formation of internal
that the Ir biphephos system was less active than the Rh bi-
phephos system (hence, the batch reactions were typically
conducted over 5 h with Rh and 20 h with Ir), but not dramati-
cally so. Indeed, the Ir biphephos system showed a non-opti-
mized hydroformylation turnover frequency (TOFHF) towards
12-oxododecanenitrile (2) of 770 mol(2)mol(Ir)À1 hÀ1 (entry 2)
that was only approximately 5 times lower than the TOFHF of
3320 hÀ1 for the analogous Rh-based system (entry 1). As men-
tioned above, Beller et al. disclosed recently that an [Ir(cod)-
acac]PPh3 (in which acac=acetylacetonato, cod=1,5-cyclo-
octadiene) catalyst was no more than 8 times slower than a Rh
catalyst in the hydroformylation of various olefins.[9a] Yet, the
activity of Ir-based catalysts in the hydroformylation of 1 was
very much dependent on the nature of the ligand: an experi-
ment performed with Ir-Xantphos proceeded significantly
more slowly (TOFHF =97 hÀ1, entry 6) than that with the Rh-
isomers (1-int) to a similar extent (ꢀ15–25% yield). Remarka-
bly, based on the results reported in Table 1, both the Rh- and
Ir-biphephos systems controlled the distribution of the internal
isomers formed, and eventually only 9-undecenitrile (major
product) and 8-undecenitrile (minor product) were generated.
The distribution of internal isomers of undecenitrile (1-int) was
determined readily by NMR analysis of the crude reaction mix-
ture. The typical signals for the internal isomers were observed
1
in H NMR (CDCl3) spectra at d=5.20–5.40 ppm for olefinic hy-
drogens and the presence of a distinct CH3CH2 triplet signal at
d=1.05 ppm evidenced isomerization products in which the
double bond had migrated over at least two carbons from the
terminal positions, that is 8-undecenitrile, 7-undecenitrile, and
possibly other internal isomers (see Figure S5). Distinct alkene
signals were also evidenced in 13C{1H} NMR spectra, enabling
determination of the trans/cis configurations of the internal
isomers (Figure 2, see also Figure S6).[22] As seen in Table 1, the
Ir-biphephos system allowed for slightly but noticeably better
control of the distribution of the internal isomers than the Rh-
biphephos catalyst, with systematically higher ratios of 9-/8-un-
decenitrile, whatever the conditions used (entries 1,3 vs. 2,4).
Thus, the internal olefins formed during the hydroformylation
of 1 were typically comprised of 90–96% 9-undecenitrile with
Ir-biphephos and 80–90% with Rh-biphephos.
Xantphos system (TOFHF =1950 hÀ1
, entry 5). Notably, the
[Pd(acac)2]/biphephos and [RuCl2(PPh3)3]/biphephos combina-
tions also proved effective, although they proceeded more
slowly than with Ir- and Rh-biphephos catalysts under the
given conditions, with TOFHF values of 210 mol(2)mol(Pd)À1 hÀ1
(entry 15) and 310 mol(2)mol(Ru)À1 hÀ1 (entry 16; see also
Table S2 in the Supporting Information). For these reasons, fur-
ther studies were focused on Ir and Rh systems.
Remarkably, the Ir- and Rh-biphephos catalysts performed
similarly well in terms of chemo- and regioselectivity in hydro-
formylation. The linear aldehyde product 2 was obtained in
73% yield with [IrCl(cod)]2/biphephos (entry 2) and in 79%
yield with [Rh(acac)(CO)2]/biphephos (entry 1), with l/b ratios
[2/10-methyl-11-oxoundecanenitrile (3)] of 99:1 in both cases.
A series of experiments were performed to evaluate the im-
portance of the excess of ligand in the hydroformylation–isom-
erization reaction of 1, regarding in particular the distribution
of internal isomers 1-int. The results are summarized in Table 2.
With [Rh(acac)CO2], [IrCl(cod)]2, and [Ir(acac)(cod)] as precur-
sors, a slight but noticeable positive effect on the selectivity
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perature, the distribution of the internal isomers was less con-
trolled and larger amounts of the undesired hydrogenation
product were formed.
The influence of the overall syngas pressure [20–80 bar (2–
8 MPa), CO/H2 =1:1] was examined under conditions optimized
specifically for Ir- and Rh-biphephos catalysts (see Table 4).
Whatever the pressure used (20 or 80 bar), the activity and se-
lectivity for linear aldehyde 2 were not significantly affected
(Table 4). However, the rate of formation of internal olefins de-
creased with pressure. With both systems, high pressure—
thus, a higher amount of CO—resulted in a better selectivity
for hydroformylation, which was favored vs. isomerization;
hence, better control over the distribution of internal isomers
in favor of 9-undecenitrile was obtained (86–95% with Rh and
90–97% with Ir). This trend was clearly observed in the olefinic
region of the 13C NMR spectra of isomerization products (see
Figure 2).
The influence of the CO/H2 ratio is summarized in Table 5.
With both Ir- and Rh-biphephos systems, an increase in the
partial pressure of CO improved the chemoselectivity and thus
the yield of aldehydes. Concomitantly, a slightly but noticeably
improved control of the internal isomers distribution was ob-
served.
Figure 2. Detail of the olefinic region of the 13C{1H} NMR spectra (125 MHz,
CDCl3, 238C) of isomerization products (cis/trans-9- and 8-undecenitrile) iso-
lated from the hydroformylation of 1 promoted by Rh-biphephos at 1208C
over 5 h at different pressures (Table 4, entries 1–4).
The influence of total and par-
tial CO pressure can be account-
Table 2. Effect of ligand loading on the internal olefin distribution in hydroformylation–isomerization of 1/1-int
ed for on the basis of the gener-
al dissociative catalytic cycle for
olefin hydroformylation first pro-
posed by Wilkinson and co-
workers (Scheme 2).[23] Increase
in the CO pressure shifts the
conversion of alkyl metal inter-
mediate II towards dicarbonyl
species III, towards the corre-
sponding acyl metal intermedi-
ate IV (and aldehyde), hence
preventing b-H elimination from
II, which eventually leads to
isomerization via hydride inter-
mediates of type V.
promoted by the Rh- and Ir-biphephos systems.[a]
Entry
Precursor
Biphephos
[equiv]0
1[b]
[%]
1-int[b]
[%]
9-/8-
undec
2+3[b]
[%]
2/3
4[b]
[%]
Conv. 1[c]
[%]
HF[d]
[%]
1
2
3
4
5
6
7
8
[Rh(acac)(CO)2]
[Rh(acac)(CO)2]
[Rh(acac)(CO)2]
[IrCl(cod)]2
[IrCl(cod)]2
[IrCl(cod)]2
20
50
100
20
50
100
20
0
1
1
0
0
18
3
36
16
17
19
22
23
16
21
13
81/19
84/16
90/10
86/14
93/7
100/0
92/8
95/5
79
77
76
73
71
60
64
43
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
5
5
4
5
6
6
12
8
99
99
99
100
100
81
83
82
81
77
75
78
70
73
[Ir(acac)(cod)]
[Ir(acac)(cod)]
97
62
100
[a] Reaction conditions unless otherwise stated: 1/1-int (95:5, 5.0 mmol), [1/1-int]0/[M]=20000, toluene (5 mL),
P=20 bar CO/H2 (1:1), T=1208C, t=5 h (Rh) or 20 h (Ir). [b] Distribution [mol%] of remaining 1 and internal al-
kenes 1-int, aldehydes 2 and 3, and hydrogenation product 4, as determined by NMR and GLC analyses.
[c] Conversion of 1. [d] Selectivity for hydroformylation products (2+3) vs. isomerization and hydrogenation.
Substrate scope
for 9-undecenitrile was observed by increasing the biphephos/
metal ratio from 20 to 100 (Table 2). Again, the control ap-
peared better if Ir precursors were used (entries 1, 4, and 7).
However, excess loading of ligand (i.e., 100 equiv) plagued the
hydroformylation catalytic activity of the Ir systems (entries 6
and 8), which was not the case with the Rh-biphephos system
(entries 1–3).
The Ir- and Rh-biphephos systems both enabled the hydrofor-
mylation–isomerization of related functionalized fatty alkenes,
such as methyl 10-undecenoate, 10-undecenal, 1-bromo-10-un-
decene, and the simple 10-undecene. Representative results
obtained with these substrates under the reaction conditions
optimized for 1 are summarized in Table 6. Good chemoselec-
tivity and excellent regioselectivity for the linear aldehydes
were observed in all cases. The relatively lower activity of Ir vs.
Rh was apparent for all substrates: although the reactions with
these other fatty alkenes were not optimized and no detailed
kinetics were determined, a comparison of the apparent TOFs
indicates that the Ir-biphephos system was approximately 2.5
(R=CH2Br), 4 (CO2Me), 7 (CH3) or 10 (CHO) times less active
The results of the influence of the reaction temperature
(100–1408C) are summarized in Table 3. Whatever the solvent
(toluene or acetonitrile) and precursor (Rh or Ir) used, the in-
crease in reaction temperature resulted, as expected, in an in-
crease in the global activity, both towards hydroformylation
and isomerization (Table 3). The selectivity in favor of linear al-
dehydes was unaffected by the reaction temperature and, in
all cases, 99% of linear aldehydes were observed. At high tem-
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Recycling of the hydroformyla-
tion catalyst
Table 3. Effect of the reaction temperature in hydroformylation–isomerization of 1/1-int promoted by Rh- and
Ir-biphephos systems.[a]
Entry Precursor
Solvent
T
1[b] 1-int[b] 9-/8-
2+3[b] 2/3
4[b] Conv. 1[c] HF[d]
Even if Ir catalysts are usually
cheaper than their Rh-based ho-
mologues, it is still essential for
industrial perspectives to recycle
the catalyst. For this purpose, we
[8C] [%] [%] undec [%]
[%] [%]
[%]
1[e]
2[e]
3[e]
4
5
6
7
8
9
[Rh(acac)(CO)2] toluene
[Rh(acac)(CO)2] toluene
[Rh(acac)(CO)2] toluene
[IrCl(cod)]2
[IrCl(cod)]2
[IrCl(cod)]2
[IrCl(cod)]2
[IrCl(cod)]2
[IrCl(cod)]2
100 26
120
140
100 70
120
140
20
21
25
7
88/12
79/21
73/27
98/2
51
72
69
21
73
66
24
75
69
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
3
5
6
2
5
6
2
4
6
73
98
100
26
100
100
32
71
77
74
84
77
70
80
80
73
2
0
toluene
toluene
toluene
acetonitrile 100 65
acetonitrile 120
acetonitrile 140
used
a
strategy based on
0
0
22
28
9
86/14
90/10
98/2
vacuum distillation as reported
in our previous study.[21] Vacuum
distillation of the crude reaction
mixture recovered in the hydro-
formylation–isomerization of 1/
1-int was readily achieved by
1
0
20
25
92/8
80/20
99
100
[a] Reaction conditions unless otherwise stated: 1/1-int (95:5, 5.0 mmol), [1/1-int]0/[M]=20000, [biphephos]0/
[M]=20, solvent (5 mL), P=20 bar CO/H2 (1:1), t=4 h (Rh) or 20 h (Ir). [b] Distribution [mol%] of remaining
1 and internal alkenes 1-int, aldehydes 2 and 3, and hydrogenation product 4, as determined by NMR and GLC
analyses. [c] Conversion of 1. [d] Selectivity for hydroformylation products (2+3) vs. isomerization and hydro-
genation. [e] Results from Ref. [21].
using
a
Kugelrohr system
[1808C, 1 mmHg (133 Pa), 5–
15 min] to yield three different
fractions containing respectively
Table 4. Effect of the overall CO/H2 pressure in hydroformylation–isomerization of 1/1-int promoted by Rh-
and Ir-biphephos systems.[a]
the internal isomers and the re-
sidual substrate, the pure alde-
hydes, and a liquid residue con-
Entry Precursor
H2/CO 1[b] 1-int[b] 9-/8-
9-trans/ 2+3[b] 2/3
4[b] Conv. 1[c] HF[d]
taining the catalyst. Notably, to
[bar] [%] [%] undec 9-cis
[%]
[%] [%]
[%]
avoid degradation of the catalyst
1
2
3
4
5
6
7
8
[Rh(acac)(CO)2] 10
[Rh(acac)(CO)2] 20
[Rh(acac)(CO)2] 40
[Rh(acac)(CO)2] 80
0
0
0
0
2
1
2
3
37
21
18
15
35
20
21
17
86/14
89/11
93/7
95/5
90/10
92/8
95/5
97/3
75/25
68/32
62/38
58/42
65/35
62/38
61/39
59/41
58
75
78
82
58
75
73
77
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
5
4
4
3
5
4
4
3
100
100
100
100
98
99
97
97
60
79
82
86
63
80
79
84
and/or the ligand, the liquid resi-
due was recycled in a controlled
atmosphere (argon). Representa-
[Ir(acac)(cod)]
[Ir(acac)(cod)]
[Ir(acac)(cod)]
[Ir(acac)(cod)]
10
20
40
80
tive results obtained by using
this procedure evidenced that it
allowed a good chemo- and re-
gioselectivity in favor of the
[a] Reaction conditions unless otherwise stated: 1/1-int (95:5, 5.0 mmol), [1/1-int]0/[Ir]=20000 and [1/1-int]0/
[Rh]=50000, [biphephos]0/[M]=20, solvent (5 mL): toluene (Rh) or acetonitrile (Ir), T=1208C, CO/H2 =1:1, t=
5 h (Rh) or 20 h (Ir). [b] Distribution [mol%] of remaining 1 and internal alkenes 1-int, aldehydes 2 and 3, and
hydrogenation product 4, as determined by NMR and GLC analyses. [c] Conversion of 1. [d] Selectivity for hy-
droformylation products (2+3) vs. isomerization and hydrogenation.
linear aldehyde over at least
5 runs with the Rh-biphephos
system and at least 3 runs with
the Ir-biphephos system, simply
by addition of a fresh charge of
ligand after each run (i.e., 20+
Table 5. Effect of the CO/H2 ratio in the hydroformylation–isomerization of 1/1-int
4ꢂ5=40 equiv total for Rh and 20+2ꢂ5=30 equiv
total for Ir; see Table 7). Good chemo- and regioselec-
tivity in favor of the linear aldehyde and 9-undeceni-
trile were obtained in the two systems. No accumula-
tion of internal olefins was observed in the reaction,
indicating that isomerization continued over the dif-
ferent runs. Just a slight decrease in selectivity for
the linear aldehyde (with a slight increase in favor of
hydrogenation) and an incomplete substrate conver-
sion were observed, respectively, in the 5th (entry 5)
and 3rd (entry 8) runs, indicating partial catalyst de-
activation at these stages. Yet, remarkable productivi-
ties were achieved in both cases (TON
ꢀ250000 mol(1/1-int)mol(Rh)À1 and 58000 mol(1/1-
int)mol(Ir)À1).
promoted by Rh- and Ir-biphephos systems.[a]
Entry Precursor
CO/H2 1[b] 1-int[b] 9-/8- 2+3[b] 2/3 4[b] Conv. 1[c] HF[d]
[%] [%]
undec [%]
[%] [%]
[%]
1
2
3
4
5
6
[Rh(acac)(CO)2] 1:1
0
0
0
2
18
20
16
21
93/7 78
85/15 71
94/6 81
95/5 73
90/10 54
96/4 38
99/1
96/4
99/1
99/1
97/3
99/1
4
9
3
4
6
1
100
100
100
97
81
45
82
74
85
79
70
88
[Rh(acac)(CO)2] 1:3
[Rh(acac)(CO)2] 3:1
[Ir(acac)(cod)] 1:1
[Ir(acac)(cod)] 1:3
[Ir(acac)(cod)] 3:1
18 22
52
9
[a] Reaction conditions unless otherwise stated: 1/1-int (95:5, 5.0 mmol), [1/1-int]0/
[M]=20000, [biphephos]0/[M]=20, solvent (5 mL): toluene (Rh) or acetonitrile (Ir), P=
40 bar CO/H2, T=1208C, t=5 h (Rh) or 20 h (Ir). [b] Distribution [mol%] of remaining
1 and internal alkenes 1-int, aldehydes 2 and 3, and hydrogenation product 4, as de-
termined by NMR and GLC analyses. [c] Conversion of 1. [d] Selectivity for hydroformy-
lation products (2+3) vs. isomerization and hydrogenation.
Conclusions
than the analogous Rh-based system, which was in line with
the observed difference with 1 (Ir approximately 5 times less
active than Rh).
The combination of an iridium(I) precursor with biphephos
ligand provides effective catalyst systems for the controlled hy-
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of the distribution of internal
olefins formed concomitantly
during the hydroformylation
step. Effective recycling of the
iridium-biphephos catalyst by
vacuum distillation in
a con-
trolled atmosphere is demon-
strated over 3 runs.
Experimental Section
General
Scheme 2. Simplified intermediates involved in the dissociative hydroformylation catalytic cycle, as proposed by
All reactions involving metal phos-
phine catalysts were performed in
an inert atmosphere (Ar) by using
standard Schlenk techniques. Sol-
vents (toluene, tetrahydrofuran,
and acetonitrile) were purified over
alumina columns by using an
MBraun system. NMP was used as
received. [Rh(acac)(CO)2] was pro-
vided by Umicore Co. and used as
received. Ir, Ru, and Pd precursors
and biphephos were purchased
from Strem Chemicals and used as
received. 10-Undecenitrile (1, 95%,
containing 5% of 9- and other
minor internal isomers), methyl 10-
undecenoate, and undecenal were
supplied by Arkema France. 11-
Bromo-1-undecene was purchased
from Sigma–Aldrich. All substrates
were purified by passage through
an alumina column and degassed
thoroughly in freeze–thaw vacuum
cycles.
Wilkinson and co-workers.[23]
Table 6. Hydroformylation–isomerization of functionalized and simple fatty alkenes promoted by the Ir- and
Rh-biphephos systems.[a]
Entry Precursor
R
t
Subs[b] int[b] 9-/8-
Ald[b] Ald
Hydrog[b] Conv. subs[c] HF[d]
[h] [%]
[%]
int
[%]
l/b
[%]
[%]
[%]
1[e]
2
[Rh(acac)(CO)2] CN
[Ir(acac)(cod)] CN
[Rh(acac)(CO)2] CO2Me
[Ir(acac)(cod)]
[Rh(acac)(CO)2] CH3
[Ir(acac)(cod)] CH3
5
20
5
0
0
0
2
12
16
22
11
13
10
5
9
14
6
81/19 79
88/12 74
80/20 82
90/10 80
85/15 75
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
5
4
7
5
3
3
4
3
2
3
4
3
3
100
100
100
98
88
53
84
68
49
83
83
78
86
86
85
85
85
76
84
80
84
88
83
3[e]
4
CO2Me 20
5[e]
6
5
20 47
48 16
5
20 51
48 17
95/5
45
90/10 71
79/21 51
7[e]
8
[Rh(acac)(CO)2] CH2Br
[Ir(acac)(cod)] CH2Br
32
91/9
92/8
41
66
1H and 13C NMR spectra were re-
corded on Bruker AC-300, AM-400,
14
10
5
9[e]
10
[Rh(acac)(CO)2] CHO
[Ir(acac)(cod)] CHO
5
15
20 39
48
90/10 71
90/10 53
90/10 76
85
61
92
1
and AM-500 spectrometers. H and
13C chemicals shifts were deter-
mined by using residual signals of
the deuterated solvents and were
calibrated against SiMe4. Signals
were assigned by using 1D (1H,
13C{1H}) and 2D (COSY, HMBC,
HMQC) NMR experiments. GLC-
flame ionization detector analyses
were recorded on a Shimadzu GC-
8
13
[a] Reaction conditions unless otherwise stated: substrate (5.0 mmol), [substrate]0/[M]=20000, [biphephos]/
[M]=20, solvent (5 mL): toluene (Rh) or acetonitrile (Ir), T=1208C, P=20 bar CO/H2 (1:1). [b] Distribution
[mol%] of remaining substrate, internal alkenes (residual or formed during the reaction), aldehydes (linear and
branched) and hydrogenation product, as determined by NMR and GLC analyses. [c] Conversion of substrate.
[d] Selectivity for hydroformylation products vs. isomerization and hydrogenation. [e] Results from Ref. [21].
2014 apparatus. Quantitative 13C NMR spectra (Figure S6) were ob-
tained in inverse gated experiments (pulse angle=908, delay=
10 s, acquisition time=1.25 s, number of scans=100–500).
droformylation–isomerization of simple and functionalized
fatty 1-alkenes. In contrast with the open literature in which
rhodium catalysts are usually considered much more active
(i.e., by several orders of magnitude) than iridium catalysts,
these iridium-biphephos catalysts are just only approximately
5 times less active than the corresponding rhodium-biphephos
systems (730 vs. 3160 hÀ1 under similar reaction conditions).
Reactions can be performed at a very high substrate/iridium
molar ratio (20000), yielding the desired linear aldehyde with
99% regioselectivity, whatever the precursor used. Interesting-
ly, the iridium-biphephos system appears slightly less isomeriz-
ing than its rhodium analogue, allowing improved control
Hydroformylation reactions
General procedure: In a typical experiment, 1 (826 mg, 5.0 mmol)
was added in Ar to a solution of the metal precursor (0.25 mmol)
and the corresponding ligand (5 mmol) in solvent (5 mL), pre-mixed
in a Schlenk flask. The solution was transferred in Ar into a 100 mL
stainless-steel autoclave, equipped with a magnetic stirrer bar. The
reactor was sealed, flushed several times with CO/H2 (1:1), charged
with CO/H2 at the desired pressure at RT, and heated in an oil bath
&
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Full Papers
[1] For leading review articles and
recent examples, see: a) Rhodium
Table 7. Recycling of the Rh and Ir biphephos systems over 5 and 3 runs, respectively, in the hydroformyla-
tion–isomerization of 1/1-int.[a]
Catalysed Hydroformylation (Eds.:
P. W. N. M. van Leeuwen, C. Claver),
Kluwer, Dordrecht, 2000; b) H. W.
Bohnen, B. Cornils, Adv. Catal.
Entry Precursor
Cycle Biphephos
excess[e] [equiv] [%] [%]
1[b] 1-int[b] 9-/8-
2+3[b] 2/3
4[b] Conv. 1[c] HF[d]
undec [%]
[%] [%]
[%]
2002, 47, 1; c) K.-D. Wiese, D. Obst,
Top. Organomet. Chem. 2006, 18, 1;
d) B. Breit (Ed.: M. J. Krische) in Top.
Curr. Chem. 2007, 279, 139; e) C. D.
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Gauß, A. Seidel, P. Torrence, P. Hey-
manns, A. Hçhn, M. Beller, J. F. Knif-
ton, A. Klausener, J.-D. Jentsch,
1
2
3
4
5
6
7
8
[Rh(acac)(CO)2]
1
2
3
4
5
1
2
3
–
5
0
0
6
5
5
6
7
20
21
20
77/23 88
75/25 89
76/24 88
72/28 86
74/26 85
99/1
99/1
99/1
99/1
98/2
99/1
99/1
98/2
6
6
7
8
8
4
4
4
100
100
100
100
100
100
98
93
94
93
91
90
80
79
79
5
5
5
–
5
5
0
0
0
0
2
5
[Ir(acac)(cod)]
93/7
92/8
94/6
76
73
71
95
A. M. Tafesh in Applied Homogene-
ous Catalysis with Organometallic
Compounds, 2nd ed. (Eds.: B. Cor-
nils, W. A. Herrmann), Wiley VCH,
Weinheim, 2008, 27; f) A. T. Axtell,
C. J. Cobley, J. Klosin, G. T. White-
[a] Initial conditions: 1/1-int (95:5, 5.0 mmol), [1/1-int]0/[M]=50000 (Rh) or 20000 (Ir), [biphephos]0/[M]=20,
solvent (5 mL): toluene (Rh) or acetonitrile (Ir), P=20 bar CO/H2 (1:1), t=72 h (Rh) or 24 h (Ir). [b] Distribution
[mol%] of remaining 1, internal alkenes 1-int (residual or formed during the reaction), aldehydes 2 and 3, and
hydrogenation product 4, as determined by NMR and GLC analyses. [c] Conversion of 1. [d] Selectivity for hy-
droformylation products vs. isomerization and hydrogenation. [e] Added in each recycling run.
ker, A. Zanotti-Gerosa, K. A.
Abboud, Angew. Chem. Int. Ed.
2005, 44, 5834; Angew. Chem.
set at the desired temperature under magnetic stirring. During the
reaction, aliquots were sampled at regular time intervals to moni-
tor the conversion and selectivities by using NMR and GLC. After
the appropriate reaction time, the reactor was cooled to RT and
vented to atmospheric pressure. The solution was analyzed by
using GLC and NMR (after evaporation of toluene). The linear/
branched (2/3) regioselectivity of aldehydes was determined by
using 1H NMR spectroscopy, based on the aldehyde resonances.
The distribution of internal isomers was determined by using 1H
and 13C NMR spectroscopy.
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Vacuum distillation of the hydroformylation reaction mix-
ture and catalyst recycling
Typical procedure: The crude hydroformylation reaction mixture
was transferred in an Ar atmosphere into a 50 mL flask. After re-
moval of the solvent under reduced pressure at RT, the mixture
was distilled in a Kugelrohr system at 1808C at 1 mmHg pressure.
Two different fractions were thus obtained: the pure hydroformyla-
tion products, which were collected in the first flask, and the cata-
lyst, recovered in solution with residual aldehydes and undeceni-
trile, in the boiler. This residual phase was collected in an inert at-
mosphere and reused, with or without addition of fresh ligand, for
a subsequent hydroformylation run.
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Supporting information
Representative 1D and 2D 1H and 13C{1H} NMR spectra for organic
compounds and additional catalytic data for Rh, Ir, and Ru-based
systems are available in the Supporting Information.
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Acknowledgements
This work was supported by Arkema France. We thank Umicore
Co. for their generous gift of [Rh(acac)(CO)2].
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Keywords: hydroformylation · iridium · isomerization · P
ligands · rhodium
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These are not the final page numbers! ÞÞ

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Received: September 30, 2014
Published online on && &&, 0000
&
ChemCatChem 0000, 00, 0 – 0
www.chemcatchem.org
8
ꢁ 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

FULL PAPERS
J. Ternel, J.-L. Couturier, J.-L. Dubois,
J.-F. Carpentier*
&& – &&
Rhodium versus Iridium Catalysts in
the Controlled Tandem
Hydroformylation–Isomerization of
Functionalized Unsaturated Fatty
Substrates
Place your bets now: Iridium-biphe-
phos catalysts are highly effective in the
controlled tandem isomerization–hydro-
formylation of 10-undecenitrile and re-
lated functionalized unsaturated fatty
substrates.
ChemCatChem 0000, 00, 0 – 0
www.chemcatchem.org
9
ꢁ 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ