Accepted Article

Title: Earth-abundant transition metals-catalyzed oxidative

transformations of bio-sourced alcohols

Authors: Duc Hanh Nguyen, Yohann Morin, Lei Zhang, Xavier Trivelli,
Frédéric Capet, Sébastien Paul, Simon Desset, Franck
Dumeignil, and Regis Gauvin

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Earth-abundant transition metals-catalyzed oxidative

transformations of bio-sourced alcohols
Duc Hanh Nguyen,[a] Yohann Morin,[a] Lei Zhang,[a] Xavier Trivelli,[b] Frédéric Capet,[a] Sébastien Paul,[a]
Simon Desset,[a] Franck Dumeignil*[a] and Régis M. Gauvin*[a]

Abstract: Catalytic acceptorless dehydrogenative oxidation of bio- point of view, the dehydrogenation of primary alcohols initially
sourced alcohols into carboxylic acid salts was achieved using earth- produces aldehydes that can further react with a nucleophile such
abundant Fe and Mn complexes featuring aliphatic PNP pincer as an alcohol or an amine, to yield a hemiacetal or hemiaminal
ligands, in good to excellent yield. The iron derivatives were intermediates that finally dehydrogenates to esters or amides,
characterized using 57Fe NMR. Mn-pincer catalysts are catalytically respectively (Scheme 1). 5 Following the similar approach,
more efficient than their Fe counterparts thanks to their robustness dehydrogenative couplings of primary alcohols in basic aqueous
under basic conditions. Attempts to generate aldehydes from alcohols media produces carboxylic acid salts in sustainable and
were not successful using Fe and Mn species, but a commercially environmentally benign manner. 6 This oxidative transformation
available Ru analogue selectively achieves this transformation under generates H2 as the only by-product.
very mild conditions, in the presence of a large excess of acetone as
hydrogen acceptor.

Introduction

The constant dwindling of fossil resources is one of the biggest

challenges for mankind in the 21st century. It mobilizes both Scheme 1. Dehydrogenative coupling reactions of primary alcohols
academia and industry to provide solutions for improvements in
operational efficiency (“drop-in strategy”) and in product
innovations (“emerging strategy”). 1 In this perspective, Several examples of “classical” organometallic complexes have
sustainable processes that explore renewable feedstocks instead been reported for this transformation. Möller et al.7 and Madsen
of crude oil have become industrially important alternatives.1 Of et al.8 showed that Ru complexes featuring monodentate carbene
particular interest are bio-based primary alcohols, which are and phosphine ligands are catalytically active for a broad
increasingly used as biofuels as well as platform molecules in the substrate scope. Prechtl et al. 9 used methylated pincer-type
production of higher added-value chemicals. 2 For example, PMeNP ruthenium complexes while Wang et al. reported a water-
bioethanol worldwide production reached 93 billion liters (which soluble binuclear Rh-terpyridine species that promotes this
currently accounts for almost 90% of the global biofuel production) reaction.10 Noteworthy, these systems do not require a hydrogen
while 1-butanol is considered as an advanced biofuel.3 acceptor although high catalyst loading (1.0-2.0% molar) and long
In this context, activation of alcohols by acceptorless reaction times (16-24h) are usually needed to achieve satisfactory
dehydrogenation reactions has gained interest as an yield.
environmentally friendly, atom-efficient catalytic process that A further category of catalysts relies on metal-ligand cooperative
allows producing a wide range of products including aldehydes, systems: the ligand plays an active role in the catalytic cycle and
ketones, acetals, esters, amides, imines, amines, and α- directly interacts with the substrate during different steps of the
functionalised carbonyl compounds.4 From the reaction pathway catalytic cycle.11 Grützmacher et al. reported a series of Rh and
Ru catalysts that involves an amino-amido pair, however requiring
a hydrogen acceptor to proceed.12 Notably, Milstein et al. reported
a Ru-based pincer [Ru(PNN)] complex remarkably active even
[a] Dr. D. H. Nguyen, Dr. Y. Morin, Dr. L. Zhang, Dr. X. Trivelli, Dr. F.
under acceptor-less conditions.13 We recently demonstrated that
Capet, Prof. S. Paul, Dr. S. Desset, Prof. F. Dumeignil, Dr. R. M.
Gauvin. pincer PHNP ruthenium complexes efficiently catalyze this
Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - reaction at low catalyst loading (0.1 mol%). 14 In addition, the
UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille, related metal-catalyzed MeOH decomposition to hydrogen and
France
CO2 via formic acid salt intermediate was extensively studied by
E-mail: [email protected], [email protected]
[b] Dr. X. Trivelli different groups.15 This study was further extended with ethanol
Univ. Lille, CNRS, UMR 8576 - UGSF - Unité de Glycobiologie and glycerol solutions to produce hydrogen, along with the
Structurale et Fonctionnelle, F-59000 Lille, France respective formation of acetic and lactic acids in selective
Supporting information for this article is given via a link at the end of manner.16
the document. Recently there has been strong interest in the challenge of
replacing the highly active and selective well-established precious

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ChemCatChem 10.1002/cctc.201700310

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metal catalysts by finding new (biocompatible) earth-abundant HMBC pulse sequence was chosen as it provides all the coupling
metal-based counterparts. 17 Indeed, use of this type of metals constants in a single experiment (1JHFe, 2JHP, 1JPFe) in addition to
would be highly beneficial in terms of sustainability and lower the 57Fe chemical shift. Indeed, 57Fe NMR resonance for both
catalysts cost. In the present contribution, catalytic conversion of stereoisomeric Fe-3a and Fe-3b are respectively determined to
bio-sourced alcohols into carboxylic acid salts was accomplished be 2645 and 2743 ppm while that for the borohydride derivative
in the presence of earth-abundant Fe and Mn complexes Fe-4 is significantly shifted to higher-field at 2133 ppm. In contrast,
supported by aliphatic PNP pincer ligands. The selective their coupling constants values 1JHFe and 1JPFe do not vary
transformation of alcohols into aldehydes by using acetone as significantly and are of about 12 and 40 Hz, respectively. So far
hydrogen acceptor was also probed with these species. only scarce examples related to one-bond 1H-57Fe scalar coupling
constant values for iron hydride complexes have been reported.21
In the course of our synthetic studies, we obtained single crystals
Results and Discussion of Fe-1 suitable for diffraction studies. The solid state structure of
this paramagnetic, 16e- penta-coordinated iron complex Fe-1 is
displayed on Figure 2. The complex features a distorted square
pyramidal geometry highly similar to one of two solvomorphs of
reported analogous compound [FeCl2(iPr2PC2H4)2NH)],22 with the
PNP framework coordinated in meridional configuration and with
one of the bromide ligands occupying the axial position. The low
degree of distortion from square pyramidal is shown by the τ value
of 0.026.23 The Fe1-N1 bond (2.2677(15) Å) is characteristic for
iron-amino moiety. The axial bromo Br1-Fe bond length
(2.5238(3) Å) is longer with respect to that of the remaining Br2-
Fe1 bond (2.4635(3) Å). The P(1) − Fe(1) − P(2) bond angle is
151.363(18)°.

Table 1. Selected NMR data (C6D6, 300K).

11
15 B 57
[Fe] N (ppm) Fe (ppm)
(ppm)

Fe-3a 56 - 2645 (1JFe-H = 12 Hz, 1JFe-P = 40 Hz)

Figure 1. Transition metal complexes used in this study. Fe-3b nd - 2743 (1JFe-H = 12 Hz, 1JFe-P = 40 Hz)

Fe-4 48 -32 2133 (1JFe-H = 10 Hz, 1JFe-P = 40 Hz)

A series of known iron (Fe-1, Fe-2, Fe-3 as a mixture of two Fe-5 47 -31 nd
stereoisomers Fe-3a and Fe-3b in 1:0.7 ratio, respectively, Fe-4
and Fe-5) and manganese (Mn-1, Mn-2, Mn-3) complexes were
selected for these studies (Figure 1).5k,4p,18 The synthesis of the
borohydride complex Fe-5 was improved by treating the dichloro
carbonyl [FeCl2(CO)((Cy2PC2H4)2NH)] complex with NaBH4
excess in EtOH/toluene mixture at room temperature since this
reaction was previously described as unselective in an
EtOH/CH3CN mixture. 19 This revisited procedure afforded the
targeted complex in a 78% yield. As complementary
spectroscopic studies, both 15N and (challenging) 57Fe NMR were
investigated (Table 1). Thanks to 1H-15N 2D HSQC NMR
sequence, 15N chemical shifts for Fe-3a, Fe-4 and Fe-5 are
respectively located at 56, 48 and 47 ppm, consistent with
nitrogen sp3 hybridization.5k Notably, we resorted to 57Fe NMR, as
valuable information may be deduced from comparison of
isotropic chemical shift of various complexes. 57Fe is a very low
sensitivity spin ½ nucleus (receptivity with respect to 13C of
4.2x10-3) with a low (2.1%) natural abundance. The very wide 57Fe Figure 2. ORTEP view of solid-state structure of Fe-1. Ellipsoids are given at
chemical shift range spreads over ca. 12 000 ppm, which makes the 50% probability level. Selected bond distances (Å) and angles (deg): Br1-
iron NMR an extremely powerful and direct probe of the Fe1 = 2.5238(3), Br2-Fe1 = 2.4635(3), Fe1-P1 = 2.5271(6), Fe1-P2 = 2.5227(6),
Fe1-N1 = 2.2677(15), N1-H1 = 0.84(2). Br1-Fe1-P1 = 101.177(14), Br2-Fe1-
asymmetry of the electron distribution around the metal.20 Very Br1 = 108.573(11), Br2-Fe1-P1 = 95.820(14), Br2-Fe1-P2 = 98.620(15), P2-
low frequency nuclei such as 57Fe can be more easily detected by Fe1-Br1 = 97.467(15), P2-Fe1-P1 = 151.363(18), N1-Fe1-Br1 = 98.50(4), N1-
indirect experiments like HSQC/HMQC/HMBC. The 1H-57Fe- Fe1-Br2 = 152.92(4), N1-Fe1-P1 = 78.08(4), N1-Fe1-P2 = 77.82(4).

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We next probed the efficiency of these readily accessible base Under similar reaction conditions, the borohydride derivative Fe-
metal compounds in the oxidation of alcohols into carboxylic acids. 4 afforded butyric acid in 58 % yield (Table 2, Entry 3). Performing
The catalytic conditions were optimized for the acceptorless the reaction for prolonged reaction times resulted in limited yield
dehydrogenative coupling (ADC) of 1-butanol and water to butyric improvement from 67% after 6 h to 74% after 17 h (Table 2,
acid salt. The catalytic reaction was initially carried out in Entries 4 and 5). Influence of the solvent was also studied, based
presence of 2 mol% of catalyst, 2 molar equiv. of water and 1.1 on observations made on related pincer systems.16c No catalytic
molar equiv. of KOH, at 120°C with toluene as a solvent. Both activity was observed when the reaction was carried out in polar
dibromo Fe-1 and dibromo carbonyl Fe-2 showed no catalytic DMSO solvent (Table 2, Entry 7) while in 1,4-dioxane, lower
activity and formed black solids after 3h (Table 2, Entries 1 and butyric acid yield of 52% was obtained with respect to toluene
2). Fe-2 was previously shown to be catalytically inactive for the (Table 2, Entry 6). This contrasts with the beneficial solvent effect
hydrogenation of esters under basic conditions.18b This contrast observed in the Fe-catalyzed conversion of glycerol to lactic acid
with the related ruthenium pincer complex [Ru(Cl)(µ- by Crabtree and Hazari.16c
Cl)((iPr2PC2H4)2NH)]2 that catalyzes this reaction under basic Very interestingly, running the reaction in the absence of water,
conditions.14 This most probably owes to the easier formation of allows not only achieving significantly improved yields, but also a
catalytically active hydrido carbonyl species under reaction more efficient isolation of the products by precipitation and
conditions (i.e. in the presence of alcohol and base) in the case extraction, as Madsen et al. very recently reported for Ru
of ruthenium compared to iron.24 systems.8 Thus, excellent isolated yield for butyric acid was
obtained (96%, Table 2, Entry 8). Lowering the catalyst loading
Table 2. Oxidation of butan-1-ol into butyric acid catalysed by Fe- and Mn-PNP from 2 to 1 mol% leads to a lower isolated yield of 68% (Table 2,
complexes. Entry 9). As observed above, 1,4-dioxane has a harmful effect on
the catalytic performance since only 69% of butyric acid was
Butyric obtained (Table 2, Entry 10). Monohydride bromo complex Fe-3
Entry [M] t(h) H2O (equiv.) Solvent
Acid (%)b
shows the similar catalytic activity (Table 2, Entry 11) than Fe-4,
1 Fe-1 3 2 Toluene 0 which suggests that both compounds generated similar catalytic
active species under reaction conditions, as already observed for
2 Fe-2 3 2 Toluene 0 Ru analogues.14 The influence of substituent groups on the
phosphorus atom of the PNP ligand was also investigated.
3 Fe-4 3 2 Toluene 58
Replacing isopropyl groups by slightly bulkier cyclohexyl ones
4 Fe-4 6 2 Toluene 67 resulted in lower isolated yield of 74% (Table 2, Entry 12).
Furthermore, it appears that iron and manganese systems are
5 Fe-4 17 2 Toluene 74
less tolerant towards water compared to the ruthenium ones. In
6 Fe-4 6 2 1,4-Dioxane 52 the latter case, we have demonstrated that ruthenium hydroxide
species reversibly forms under these conditions, being able to
7 Fe-4 6 2 DMSO 0 regenerate the catalytically active amido species with water
elimination.14 It may well be that this phenomenon (trapping of the
8 Fe-4 6 0 Toluene 96
active form of the catalyst by H2O) is not reversible in the Fe and
9a Fe-4 6 0 Toluene 68 Mn systems, or that it irreversibly leads to deactivation species.
When discussing the compared activity of compounds Fe-1, Fe-
10 Fe-4 6 0 1,4-Dioxane 69
2, Fe-3 and Fe-4, one can rationalize these in term of active
11 Fe-3 6 0 Toluene 89 species generation. Indeed, in the present case, it is assumed that
the entry into the catalytic cycle is the penta-coordinated
12 Fe-5 6 0 Toluene 74 [Fe(H)(CO)((iPr2PC2H4)2N)] species bearing the PNP ligand in its
amido form. As mentioned above, the carbonyl derivative Fe-2
13 Mn-2 24 2 Toluene 12
does not generate a hydrido carbonyl species. Thus, even if Fe-1
14 Mn-2 24 0 Toluene 95 would form Fe-2 by alcohol decarbonylation, the reaction would
not proceed further. On the other hand, HBr elimination from Fe-
15 Mn-3 24 0 Toluene 94 3 affords the amido species,18b, 25 while BH3 release from Fe-4
16 Mn-1 24 0 Toluene 89
generates a dihydride species [Fe(H)2(CO)((iPr2PC2H4)2NH)] and
thus leads into the catalytic cycle.26
17 Mn-3 24 0 1,4-Dioxane 50 Next, manganese complexes were catalytically evaluated. This
base metal has attracted considerable attention for related
18 Mn-4 24 0 Toluene 91
transformations. 27 In our recent report on the acceptorless
dehydrogenation coupling of alcohols into esters, the active
Reaction conditions: [M] = 0.05 mmol (2 mol%), n(butan-1-ol) = 2.5 mmol
(185.3 mg), n(H2O) = 0-2 molar equiv., n(KOH) = 2.75mmol (154 mg), amido dicarbonyl species Mn-2 was shown to be thermally very
V(toluene) = 3 mL. 120°C, under argon. a: [M] = 1 mol%. Yield measured by robust compared to the analogous Fe complex. 5p Under
1
HNMR. b: Yield in butyric acid, Entries 1-7: Determined by NMR, Entries 8-18: previously established standard reaction conditions (2 mol%
Isolated yield.
catalyst loading, 120 °C, 2 molar equiv. water, 1.1 molar equiv.

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ChemCatChem 10.1002/cctc.201700310

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KOH), Mn-2 displays a low catalytic activity as only 12% of butyric catalytically efficient since conversions up to 96% were reached
acid yield was obtained after 24 h (Table 2, Entry 13). Remarkably, after 24 h (Table 3, Entries 6 and 8). Both Fe-4 and Mn-2 were
in the absence of water, excellent isolated yield up to 95% was evaluated for oxidation of more reactive conjugated geraniol and
achieved (Table 2, Entry 14). Using both chloro Mn-1 and nerol substrates. Theses reactions however proceed in
borohydride Mn-3 precatalysts produced also butyric acid with unselective manner and mixtures of unidentified products were
very good isolated yield of 89 and 94%, respectively (Table 2, obtained. The (S)-(-)-perillyl alcohol was converted into a mixture
Entries 15 and 16). In addition, as already observed for Fe-based of the perrilic acid and reduced dihydroperillic derivative in 44 and
catalysts, replacement of toluene as the solvent by 1,4-dioxane 50% isolated yields with respective ratio of around 1:10 in
induced production of butyric acid with a lower yield of 50% (Table presence of Fe-4 and Mn-2, respectively (Table 3, Entries 9 and
x, Entry 17). 10).
From the mechanistic point of view, oxidation of primary alcohols
Table 3. Oxidation of bio-sourced alcohols to acid salts catalysed by Fe- and to carboxylic acid salts can proceed by an initial alcohol
Mn-PNP complexes. dehydrogenation step to form an aldehyde intermediate. From
this point on, at least three distinct reaction pathways can take
Entry Substrates [M] Products Yield (%)a place (Scheme 2). In Path 1, the aldehyde reacts with water or
/and OH- to afford a hydrate that is subsequently dehydrogenated
67 and deprotonated into the carboxylic acid salt.13, 29 , 30 Path 2
1 Fe-4
(49)
consists of an ADC reaction which yields an ester that is then
99 saponified.14 In Path 3, the aldehyde intermediate undergoes a
2 Mn-2
(50) Cannizzaro reaction to form a carboxylic acid and an alcohol.8
Since we did not observe any traces of esters formed, the second
91
3 Fe-4 pathway can be excluded under our reaction conditions.
(52)
Regarding Path 3, the lack of crotonization products in the case
99 of aldehyde featuring protons in the  position is a strong
4 Mn-2
(52) indication that this pathway is not significantly operative.

5 Fe-4 50

96
6 Mn-2
(51)

7 Fe-4 51

97
8 Mn-2
(50)

9 Fe-4 (44)

(50),
10 Mn-2
(1:10 ratio) Scheme 2. Reaction pathways for alcohol dehydrogenative oxidation

Reaction conditions: [M] = 2mol%, n(Substrate) = 2.5 mmol, n(KOH) = 2.75

mmol (154mg), V(toluene) = 3mL, 120°C, under argon. Yield measured by
1
Recording the 31P NMR spectrum of the reaction mixture at the
HNMR. Isolated yield: (In parentheses). Reaction time is 6 h with Fe-4 and 24
h with Mn-2. end of butanol dehydrogenative oxidation catalytic run revealed
the presence of the active Mn-2 species and a new manganese
Alcohols oxidation was extended to other bio-sourced alcohols compound of formula [Mn(OCOC3H7)(CO)2((Ph2PC2H4)2NH)]
such as fatty and terpenoic derivative alcohols (Table 3). In the (Mn-4) as the main organometallic species (75%), in respective
presence of Fe-4 and at 120°C, stearyl and oleyl alcohols are ratio of 1.4:1. Interestingly, in a closely related study devoted to
respectively converted to stearic and oleic acids in 67 and 99% the Mn-catalyzed ADC reaction of butanol (Mn-2, 0.6 mol%,
yield after 6h (Table 3, Entries 1 and 3). The different reactivity 130 °C, 72h),5p we also identified Mn-4 as the sole complex
can be attributed to the lower solubility of stearyl alcohol with present in the solution.
respect to that of its unsaturated counterpart (oleyl alcohol). In the Complex Mn-4 was isolated and fully characterized by
presence of Mn-2 and under similar conditions (though with multinuclear NMR and IR spectroscopies and X-ray molecular
longer reaction times), both stearyl and oleyl alcohols are structure determination. 1H NMR displays a broad triplet centered
completely converted into the corresponding acids within 24h at 8.96 ppm (JHH = 12 Hz) that is assigned to the NH hydrogen.
(Table 3, Entries 2 and 4). 28 Dihydrocitronellol and β-citronellol Such low-field resonance signal is in line with a hydrogen bonding
are transformed into the corresponding dihydrocitronellic and β- established between the N-H and the carboxylato ligand. 31P{1H}
citronellic acids with 50% yield when using Fe-4 as catalyst during spectrum shows a singlet at 88.1 ppm. The 15N resonance is
6 h (Table 3, Entries 5 and 7). Interestingly, Mn-2 proved to be located at 39.3 ppm according to 1H-15N 2D HSQC NMR, which

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ChemCatChem 10.1002/cctc.201700310

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is consistent with the sp3 hybridization for the amino nitrogen atom. As this compound was obtained from ADC of butanol, it can be
On the 13C{1H}, since 13C and 55Mn resonance frequencies are assumed that it originates from reaction of intermediate aldehyde
very close (respectively 100.6 and 99.24 MHz at 9.4 T), leading with adventitious water, forming an aldehyde hydrate which can
to an efficient scalar relaxation mechanism that broadens the 13C be dehydrogenated into butyric acid. This acid can in turn react
signal of carbonyl ligands directly bound to the Mn center, their with Mn-2 to afford Mn-4. Indeed, this complex was independently
chemical shifts were therefore not determined.5p The carboxylate synthesized in moderate isolated yield (67%) by reaction of Mn-2
group however resonates as a singlet at 185.23 ppm. with 1.5 equiv. of butyric acid. Interestingly this shows a
In the solid-state, IR spectrum shows two intense characteristic decomposition pathway for this catalytic system when applied to
bands at 1915 and 1822 cm-1 that are assigned to two CO ligands ADC. Although this species is no longer active for ADC reactions
in mutually cis-position. The IR stretching C=O frequency of the under base-free conditions, it could be involved within a catalytic
carboxylate ligand is located at 1563 cm-1. In addition, N-H cycle of the manganese-catalyzed alcohols oxidation process to
stretching band is observed at 3095 cm-1. The solid-state carboxylic acid salts. The efficiency of the carboxylato Mn-4
molecular structure features a distorted octahedral geometry, complex for the oxidation of butan-1-ol was assessed. It afforded
similar to that of [Mn(OCOH)(CO)2((Ph2PC2H4)2NH)] reported by a 91% yield of butyric acid (Table 2, Entry 18). Consistently, after
Boncella et al. 31 The PNP tridentate ligand is coordinated in a few minutes of reaction, the reaction mixture color turned from
meridional fashion. The two terminal carbonyl ligands are in yellow to dark red, which may indicate that Mn-4 generates the
mutually cis configurations, one being trans to the amino moiety. (red) catalytic species Mn-2 under basic conditions.
The residual position is occupied by the butyrato ligand, which is As mentioned above, the first step of the alcohol oxidation
arranged in syn configuration with the N-H function (Figure 3). An process consists of an alcohol dehydrogenation step to form an
intramolecular hydrogen bond is established between the aldehyde intermediate. Aldehydes are also compounds of interest,
butyrate carbonyl oxygen and the N−H proton of the PNP ligand. and therefore their selective production from alcohols is most.
The hydrogen bond distance and the corresponding angle N1- Attractive. Although no aldehyde traces were detected under
H1···O4 are 1.965(3) Å and 158.94(3)°, respectively. carboxylic acid production conditions, very low quantities of this
compound (usually accounting for less than 1.0 %) are observed
during Ru- and Mn-catalyzed ADC reactions of alcohols into
esters.5k,5p Indeed, the ADC reactions proceed throughout several
reversible steps that includes the aldehyde consumption reaction
with a second alcohol molecule to reversibly give an unstable
hemiacetal. In order to be able to produce aldehydes instead of
esters, the formation of the intermediate hemiacetal needs to be
impeded. This can be accomplished by dilution of the reaction
medium. Moreover, to avoid the aldehyde hydrogenation reaction
which is promoted by dihydride [M(H)2(CO)((R2PC2H4)2NH)] (M =
Ru, Fe) or monohydride [Mn(H)(CO)2((R2PC2H4)2NH)] species,
the concentration of these compounds has to be maintained as
low as possible. By using a sacrificial hydrogen acceptor, these
species could be therefore converted to the corresponding amido
[M(H)(CO)((R2PC2H4)2N)] (M = Ru, Fe) or Mn-2 counterpart. As a
reference point, some Ir-, Rh- and Ru- based catalytic systems
have been found to efficiently dehydrogenate alcohols to
corresponding aldehydes.32

Figure 3. ORTEP view of solid-state structure of Mn-4. Ellipsoids are given at

the 50% probability level. Selected bond distances (Å) and angles (deg): Mn1-
P1 = 2.2926(9), Mn1-P2 = 2.2882(9), Mn1-O3 = 2.067(2), Mn1-N1 = 2.127(2), Figure 4. Ru complex used for dehydrogenation of butan-1-ol to butan-1-al.
Mn1-C18 = 1.783(3), Mn1-C17 = 1.750(3), N1-H1 = 0.90(4), O2-C18 = 1.161(4),
O1-C17 = 1.181(4), P2-Mn1-P1 = 164.68(4), O3-Mn1-P1 = 88.58(6), O3-Mn1-
P2 = 86.25(6), O3-Mn1-N1 = 90.72(9), N1-Mn1-P1 = 82.54(7), N1-Mn1-P2 =
The dehydrogenation of butan-1-ol to butyraldehyde was
83.11(7), C18-Mn1-P1 = 97.16(10), C18-Mn1-P2 = 97.21(10), C18-Mn1-O3 =
89.56(11), C18-Mn1-N1 = 179.58(13), C17-Mn1-P1 = 92.79(11), C17-Mn1-P2 examined using commercially available borohydride Ru-MACHO-
= 93.07(11), C17-Mn1-O3 = 177.04(11), C17-Mn1-N1 92.06(12), C17-Mn1-C18 BH (a pre-catalyst for ADC5 and alcohol oxidation14 reactions,
= 87.67(14). Figure 4) and in the presence of acetone as both a hydrogen
acceptor and a diluent (Table 4). When the reaction was carried
out under mild conditions (60°C, 5 mL of acetone) and in the

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ChemCatChem 10.1002/cctc.201700310

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presence of 1.0 mol% of Ru-MACHO-BH, both butyraldehyde amounts were detected after 5 h (Table 4, Entries 12 and 13).
and butyl butyrate were formed, and their respective ratio evolved This may be due to their intrinsically lower activity compared to
over time (Table 4, Entries 1-5). At very short reaction times, (15 ruthenium catalysts, as already observed in the case of ADC
minutes), butyraldehyde is the major product with a yield of 19% reactions.5k,o,p
while the yield of butyl butyrate is of 13% (Table 4, Entry 1). As
the reaction proceeds, the amount of butyraldehyde decreases
and the yield into butyl butyrate increases (Table 4, Entries 2-5). Conclusions
This indicates that under such conditions, butyraldehyde can still
further react with butan-1-ol to give the hemiacetal that is We have shown that pincer complexes of earth-abundant metals
dehydrogenated to butyl butyrate. However, compared with neat iron and manganese readily catalyse the acceptorless
conditions5k (without acetone added), the final amount of dehydrogenative oxidation of (bio-sourced) alcohols into their
butyraldehyde is higher (6%, Table 4, Entry 5) indicating that the corresponding carboxylic acid salts, under basic conditions.
addition of acetone can have a beneficial influence on the Compared to the parent Ru catalysts, the Fe and Mn systems
selectivity toward aldehyde. needed to be used in the absence of water to reach high yields.
The manganese catalysts proved to be more efficient than their
Table 4. Dehydrogenation of butan-1-ol to butyraldehyde. iron counterparts, which was ascribed to their higher robustness
under the considered reaction conditions.
Butyl In addition, as this oxidative transformation proceeds via an
Acetone n-Butanal
Entry [M] t(h) butyrate
(mL) (%)
(%)
aldehyde intermediate, we explored the option to switch the
selectively of the systems towards this compound. Thus, the
1† 0.25 19 13 commercially-available Ru-MACHO-BH has been found to be
able to selectively oxidize alcohols into aldehydes in presence of
2 0.5 13 30
a large excess of acetone as hydrogen under very mild conditions
3 Ru-MACHO-BH 5 1 10 50 while Mn- and Fe analogues feature only low activity.

4 2 7 59

5 3 6 71 Experimental Section
6 0.5 49 0 Experimental Details. All experiments were carried out under argon
atmosphere using a glovebox or a vacuum line using standard Schlenk
7 1 66 0 techniques unless some special conditions are pointed out. All ruthenium
complexes and tridentate ligands were stored under argon. GC–FID/MS
8 2 73 3
was carried out on Agilent 7890A (flame ionization detector and MS
Ru-MACHO-BH 90
9 3 70 4 detector) instruments equipped with a Zebron ZB-Bioethanol column (30
m column length x 0.25 mm internal diameter x 1.00 μm film thickness)
10 4 69 4 with helium as carrier gas. All NMR spectra were recorded on Bruker
Avance 300/400 NMR spectrometers. 1H and 13C NMR chemical shifts are
11 5 70 5 reported in ppm (δ) downfield from tetramethylsilane, 31P NMR chemical
shifts are reported in ppm (δ) and referenced to an external 85 % solution
12 Fe-4 90 5 2 0 of phosphoric acid in D2O, 15N NMR chemical shifts are reported in ppm
(δ) downfield from an external liquid ammoniac. 11B NMR chemical shifts
13 Mn-2 90 5 6 0
are reported in ppm (δ) and referenced to external solution of BF3.Et2O,
Common abbreviations used in the NMR experiments are as follows: b,
Catalytic conditions. [M] = 1 mol% (0.011 mmol), n(butan-1-ol) = 1;1 mmol
broad; s, singlet; d, doublet; t, triplet; q, quartet; sp, septet; m, multiplet; v,
(81mg, 0.1 mL), applied temperature = 60 °C, under argon, Yield determined by
virtual. Spectral assignments were made by means of routine one- (1H,
GC. 1
H{31P), 31P{1H}, 13C{1H], 13C JMOD, 11B, 11B{1H}) and two-dimensional
Noteworthy, when a very large amount of acetone (90 mL) is used, (1H-1H COSY, 1H-1H NOESY, 1H-13C HSQC, 1H-13C HMBC, 1H-15N HSQC,
1H-15N HMBC…) NMR experiments where appropriate. IR spectra were
butyraldehyde is obtained as the major product (Table 4, Entries
recorded on a Nicolet 6700 FT-IR spectrometer equipped with a Praying
6-11). Butyraldehyde is initially obtained as the sole product in 49
Mantis mirror chamber (from Harrick Scientific) by using a DRIFT cell
and 66% yield after 0.5 and 1h, respectively (Table 4, Entries 6 equipped with KBr windows. The samples were prepared under argon in
and 7). A small amount of ester builds up only after 2 h and a glove-box. Typically, 64 scans were accumulated for each spectrum
marginally varies from 3 to 5% yield after 5 h (Table 4, Entries 8- (resolution 4 cm-1). Data are reported as follows: weak (w), medium (m),
11). After 5 h, the yield into aldehyde reaches 70% while that to strong (s) and very strong (vs).
ester is kept as low as 5%. In fact, under much diluted conditions
(very large excess of acetone) the chemo-selectivity can be 57Fe NMR measurements: 57Fe chemical shifts are reported in ppm (δ) and
switched toward the production of aldehyde since aldehyde- referenced to external (liquid) Fe(CO)5. The duration of the 57Fe 90° pulse
consuming reactions are inhibited. (39.85us) was calibrated using the 73Ge NMR signal of GeCl4 with one
drop of C6D6, since this signal is readily observed in 32 scans (receptivity
Using the same reaction conditions, both Fe-4 and Mn-2 are
with respect to 13C 0.62) and the resonance frequency of 73Ge (13.96 MHz)
significantly less active than Ru-MACHO-BH: Very low aldehyde

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ChemCatChem 10.1002/cctc.201700310

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is reasonably close to that of 57Fe (12.96 MHz). 33 Very low frequency -OOCCH2CH2CH3), 18.85 (s, 2C, -CH3, PNP), 18.00 (s, 2C, -CH3, PNP),
nuclei such as 57Fe can be more easily detected by indirect experiments 14.76 (s, 1C, -CH3, -OOCCH2CH2CH3). 15N{1H} HSQC NMR (300K, C6D6,
like HSQC/HMQC/HMBC. The 1H-57Fe-HMBC pulse sequence was 40.565 MHz, ppm): δ 39.3 (1N). Anal. Calcd. For C22H44MnNO4P2: C
chosen to obtain 57Fe chemical shifts and all the coupling constants in a 52.48; H 8.81; N 2.78. Found: C 50.70; H 8.92; N 2.78.
single experiment (1JHFe, 2JHP, 1JPFe). The 1H-57Fe-HMBC spectra were
recorded assuming an apparent 15 Hz coupling constant value with a 0.5 Standard procedure for catalytic experiments: In a glovebox, the
s acquisition time, a 6 s recycling delay and 256 scans. required amount of potassium hydroxide (typically 1.1 equiv., 179 mg) and
catalyst (0.05 mmol) are weighted in a Schlenk tube containing a stir bar.
All compounds were purchased from commercial suppliers. The Under argon, the required amount of alcohol (2.5 mmol), water (2 molar
substrates and solvents were degassed by argon flushing upon use. equiv.) and toluene (3 mL) are added. The Schlenk tube is equipped with
Deuterated solvents were provided by Eurisotop and distillated prior to use. a reflux condenser topped with an argon bubbler. The system is heated
Ruthenium [Ru(H)(Cl)(CO)(PPh3)3] and using an oil bath and stirred magnetically. After the desired reaction time,
[Ru(H)(BH4)(CO)((Ph2PC2H4)2NH)] (trade name: Ru-MACHO-BH) water is added (5 mL) and the mixture is acidified using hydrochloric acid
complexes, iron FeBr2 and FeCl2, manganese [Mn2(CO)10] and and extracted with diethyl ether (5 x 10 mL). The combined organic phase
[MnBr(CO)5] complexes (Strem Chemicals) were stored inside an argon- was dried over anhydrous MgSO4 and diethyl ether was removed by rotary
filled glove box and used as received. Ligands (iPr2PC2H4)2NH, evaporator. The conversion was determined by 1H NMR spectroscopy
(Cy2PC2H4)2NH (Strem Chemicals) were stored inside an argon-filled from the crude products, in comparison with spectra of pure products
glove box and used as received. [FeBr2((iPr2PC2H4)2NH)] (Fe-1),18a,b reported in the literature. For isolated yields: the crude reaction suspension
[FeBr2(CO)((iPr2PC2H4)2NH)] (Fe-2),18a,b [FeH(Br)(CO)((iPr2PC2H4)2NH)] was filtered and the obtained solids were washed with n-pentane (3x5mL)
(Fe-3),18b [FeH(BH4)(CO)((iPr2PC2H4)2NH)] (Fe-4),18a,b and diethyl ether (2x5mL) and dissolved in water (5mL). The carboxylic
[Fe(Cl)2(CO)((Cy2PC2H4)2NH)],22 [Mn(Br)(CO)2((iPr2PC2H4)2NH)] (Mn- acid product was extracted as described above.
1),18c [Mn(CO)2((iPr2PC2H4)2N)] (Mn-2),5p
[Mn(BH4)(CO)2((iPr2PC2H4)2NH)] (Mn-3),5p were prepared following X-ray Structure Determination. A single crystal of each compound was
literature procedures. mounted under inert perfluoropolyether wax on a Mitegen MicroLoopTM.
Single-crystal X-rays measurements were performed at 100K under N2
Synthesis [FeH(BH4)(CO)((Cy2PC2H4)2NH)] (Fe-5). To a suspension of stream from a Cryostream 700 device (OxfordCryosystems). Data were
[Fe(Cl)2(CO)((Cy2PC2H4)2NH)] (0.2g) in a toluene/ethanol mixture (1/2 collected using an Apex II CCD 4K Bruker diffractometer (λ = 0.71073 Å).
ratio, 30 mL) was added in excess sodium borohydride (5 equiv. ) at 0°C. The structures were solved using SHELXT35 and refined by least-squares
The resulting reaction mixture was stirred at room temperature for 24h. procedures on F2 using SHELXL2014.36 All Hydrogen atoms were placed
The yellow suspension thus obtained was evaporated to dryness under in theoretical positions and refined riding on their parent atoms. ORTEP
reduced pressure. The product was extracted with toluene (3x15mL) and drawings were generated with ORTEP-3. 37 Crystallographic data have
the combined organic phases were collected and filtered through a short been deposited at the Cambridge Crystallographic Data Centre as
celite column. The solvent was removed under reduced pressure to afford Supplementary Publication Nos. CCDC 1532717-1532718. Copies of the
a yellow solid which was washed with n-pentane (3x15mL) and dried under data can be obtained free of charge on application to the Director, CCDC,
vacuum. Yield 0.14 g (78%). NMR data are in agreement with those 12 Union Road, Cambridge CB2 1EZ, U.K. (fax, (+44) 1223- 336-033; e-
reported in the literature.34 mail, [email protected]).

Synthesis of [Mn(OCOC3H7)(CO)2((Ph2PC2H4)2NH)] (Mn-4). To a red

solution of the manganese amido [Mn(CO)2((iPr2PC2H4)2N)] complex (Mn-
Acknowledgements
1, 154 mg) in toluene (4mL) was slowly added a solution of butyric acid
(80 mg) in toluene (2mL) at room temperature and under stirring. The
resulting reaction mixture turned immediately bright yellow. It was stirred This work was performed in partnership with the SAS PIVERT,
for 2h and evaporated under reduced pressure to afford a yellow oily-solid within the frame of the French Institute for the Energy Transition
which was washed with n-pentane (3x5mL) and dried under vacuum. A (Institut pour la Transition Energétique (ITE) P.I.V.E.R.T.
single crystal suitable for X-ray determination was obtained from (www.institut-pivert.com) selected as an Investment for the Future
crystallization from pentane. Yield (0.185g, 67%). FT-IR (KBr, cm-1): ν(NH) (“Investissements d’Avenir”). This work was supported, as part of
= 3090 (m), ν(CO) = 1915 (s), 1821.9 (s), ν(OCO) = 1562.6 (s). 1H NMR
the Investments for the Future, by the French Government under
(300 K, C6D6, 400.33 MHz, ppm): δ 8.96 (t, 1H, NH, JHH = 12 Hz, PNP),
2.84 (m, 2H, >CH2, PNP), 2.26 (t, 2H, >CH2, JHH = 7.3 Hz, - the reference ANR-001-01. L. Zhang thanks the China
OOCCH2CH2CH3), 2.23-1.98 (m, 6H, 2H of CH2 and 4H of –CH, PNP), Scholarship Council (CSC 2011008127) for providing the financial
1.84-1.69 (m, 4H, >CH2, 2H of -OOCCH2CH2CH3 and 2H of PNP), 1.62 support of his PhD. CNRS, Chevreul Institute (FR 2638),
(m, 2H, >CH2, JHH = 5.6, 14.3 Hz, PNP), 1.47 (td, -CH3, JHH = 7.3 Hz, JHP Ministère de l’Enseignement Supérieur et de la Recherche,
= 7.3 Hz, PNP), 1.34 (td, -CH3, JHH = 6.9 Hz, JHP = 7.0 Hz, PNP), 1.22 (td, Région Nord – Pas de Calais and FEDER are acknowledged for
-CH3, JHH = 7.1 Hz, JHP = 7.1 Hz, PNP), 1.04 (td, -CH3, JHH = 7.2 Hz, JHP =
supporting and partially funding this work.
7.1 Hz, PNP), 0.98 (t, 3H, -CH3, JHH = 7.2 Hz, -OOCCH2CH2CH3). 31P{1H}
NMR (300K, C6D6, 162.057 MHz, ppm): δ 88.05 (s, 2P). 13C{1H} NMR
(300K, C6D6, 100.663 MHz, ppm): δ nd (CO), 185.23 (s, 1C, -OOC, - Keywords: iron • manganese • ruthenium • carboxylic acid •
OOCCH2CH2CH3), 52.75 (t, 2C, >CH2, JCP = 6.2 Hz, PNP), 42.29 (s, 1C, alcohol• pincer ligands
>CH2, -OOCCH2CH2CH3), 27.88 (t, 2C, >CH2, JCP = 6.0 Hz, PNP), 26.72
(t, 2C, >CH-, JCP = 7.4 Hz, PNP), 24.60 (t, 2C, >CH-, JCP = 9.9 Hz, PNP),
20.59 (s, 2C, -CH3, PNP), 20.38 (s, 2C, -CH3, PNP), 19.96 (s, 1C, >CH2,

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ChemCatChem 10.1002/cctc.201700310

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Entry for the Table of Contents

FULL PAPER
Acceptorless dehydrogenative Duc Hanh Nguyen, Yohann Morin, Lei
oxidation of bio-sourced alcohols Zhang, Xavier Trivelli, Frédéric Capet,
into carboxylic acid salts was Simon Desset, Franck Dumeignil* and
achieved using earth-abundant Fe Régis M. Gauvin*
and Mn PNP complexes. Tuning of
reaction conditions allows selective Page No. – Page No.
production of aldehydes from
Earth-abundant transition metals-
alcohols using a Ru catalyst, while
catalyzed oxidative transformations
Fe and Mn species proved not
of bio-sourced alcohols.
effective.

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ChemCatChem 10.1002/cctc.201700310

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