1,2-Addition of Formic or Oxalic Acid to -N{CH2CH2(PiPr2)}2-Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid

Article abstract of DOI:10.1021/acs.organomet.6b00274

(PN^HP)Mn(CO)₂ (I) carboxylate complexes (PN^HP = HN{CH₂CH₂(PiPr₂)}₂) were prepared via 1,2-addition of either formic or oxalic acid to (PNP)Mn(CO)₂ (PNP = the deprotonated, amide form of the ligand ^-N{CH₂CH₂(PiPr₂)}₂). The structural and spectral properties of these complexes were compared. The manganese formate complex was found to be dimeric in the solid state and monomeric in solution. Half an equivalent of oxalic acid was employed to form the bridging oxalate dimanganese complex. The catalytic competencies of the carboxylate complexes were assessed, and the formate complex was found to decompose formic acid catalytically. Both dehydrogenation and dehydration pathways were active as assessed by the presence of H₂, CO₂, and H₂O. The addition of LiBF₄ exhibited a strong inhibitory effect on the catalysis.

Full text of DOI:10.1021/acs.organomet.6b00274

Communication
pubs.acs.org/Organometallics
1
,2-Addition of Formic or Oxalic Acid to
−
N{CH CH (PiPr )} ‑Supported Mn(I) Dicarbonyl Complexes and the
2
2
2 2
Manganese-Mediated Decomposition of Formic Acid
Aaron M. Tondreau and James M. Boncella*
Chemistry Division, Los Alamos National Laboratory, MS J514, Los Alamos, New Mexico 87545, United States
*
S Supporting Information
H
H
ABSTRACT: (PN P)Mn(CO) (I) carboxylate complexes (PN P =
2
HN{CH CH (PiPr )} ) were prepared via 1,2-addition of either formic or
2
2
2
2
oxalic acid to (PNP)Mn(CO) (PNP = the deprotonated, amide form of the
2
ligand −N{CH CH (PiPr )} ). The structural and spectral properties of
2
2
2
2
these complexes were compared. The manganese formate complex was
found to be dimeric in the solid state and monomeric in solution. Half an
equivalent of oxalic acid was employed to form the bridging oxalate
dimanganese complex. The catalytic competencies of the carboxylate
complexes were assessed, and the formate complex was found to decompose
formic acid catalytically. Both dehydrogenation and dehydration pathways
were active as assessed by the presence of H , CO , and H O. The addition of LiBF exhibited a strong inhibitory effect on the
2
2
2
4
catalysis.
atalytic storage and release of dihydrogen from small
C
molecules has been explored as an alternative energy
1
source. Relevant to this work is the recent progress made in
the dehydrogenation of formic acid (FA) to yield H and CO .
2
2
The original exploration of FA decomposition focused on
2
3
4
5
heavier metals such as ruthenium, rhodium, and iridium.
Figure 1. Comparison of isoelectronic metal complexes of Fe(II) and
Mn(I).
Beller was then able to extend FA decomposition to iron,
followed by other groups using pincer ligands. Several studies
by Beller and Laurenczy have explored the fundamental
properties of this reaction with iron. PN P (PN P =
HN{CH CH (PiPr )} )-supported ruthenium was also shown
to be particularly active as an alcohol dehydrogenation catalyst.
The analogous PN P-supported iron complex (PN P)Fe(H)-
CO)(CO H) was shown to be effective in the decomposition
of formic acid and methanol/water dehydrogenation. Hazari
6
7
H
H
use, the formation of two moles of gas from one mole of liquid
(
FA) prompted this investigation. Our PV-work requires lower
2
2
2
2
8
temperatures than most of the previously described reaction
conditions (typically 90 °C or higher). Attempting the catalysis
with a PNP-supported Mn(I) complex has allowed us to
investigate an alternative system under conditions that are more
amenable to our desired reaction conditions.
H
H
(
2
9
and Bernskoetter also first reported the importance of Lewis
9b
acids in the catalysis of FA decomposition. This is a pointed
example of how iron compounds have the ability to achieve
catalytic transformations that previously had been performed by
noble metals.
RESULTS AND DISCUSSION
■
Ozerov’s previous attempts to obtain a similar amido
manganese dicarbonyl with the analogous diarylamido-based
PNP ligand resulted in a mixture of di- and tricarbonyl
H
As iron compounds supported by PN P have successfully
1
1
H
manganese complexes (Scheme 1a). Our synthesis of
mirrored the FA decomposition catalysis of PN P-supported
iPr
H
(
PN P)Mn(CO) Br obviates the isolation of a tricarbonyl
ruthenium compounds, we sought to extend similar reactivity
to isoelectronic Mn(I) complexes supported in a similar
fashion. An easy extension of the iron(II) hydride/PNP amide
is to use the isoelectronic Mn(I) dicarbonyl complex (Figure
2
iPr
H
complex by forming ( PN P)Mn(CO) Br, which is primed
2
for a dehydrohalogenation that yields the five-coordinate
manganese dicarbonyl in pure form. The dehydrohalogenation
iPr
H
iPr
H
of ( PN P)Mn(CO) Br was achieved using one equivalent of
1
(
). We recently reported the synthesis of ( PN P)Mn-
2
1
0
sodium tert-butoxide (Scheme 1b) to give the desired complex
CO) Br. The desired amide complex was formed in a simple
dehydrohalogenation step, giving ( PNP)Mn(CO) .
2
iPr
iPr
( PNP)Mn(CO) (1).
2
2
We are interested in FA decomposition as a source of gas
pressure to perform pressure−volume work (PV-work), e.g., to
move an actuator. Although our end-goal differs from fuel cell
Received: April 6, 2016
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.6b00274
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Communication
Scheme 1. (a) Previous Synthesis of (PNP)Mn dicarbonyl
Scheme 2. Summary of 1,2-Addition of FA to 1 to Yield 2
with the Isolated Yield
Complex; (b) Summary of the Formation of
iPr
(
PNP)Mn(CO) with the Isolated Yield
2
resonances for the pair of carbonyl ligands (230.8 and 229.2
ppm), and their IR stretching frequencies are 1916 and 1828
−1
cm . These data are consistent for the 1,2-addition product of
iPr
H
formic acid ( PN P)Mn(OCHO)(CO) (2). A solid-state
2
structure of 2 was obtained (Figure 3) in order to assess bond
distance changes relative to 1 and to unambiguously confirm
the structure of 2.
Large red blocks of pure 1 were isolated on the gram scale
from hexane, making it an easily synthesized, scalable starting
1
13
material. The H and C NMR spectra of 1 were consistent
with a C2v symmetric molecule, with one signal for the
isopropyl methyl carbon and hydrogen atoms and only one
1
3
signal for the carbonyl ligands at 234.8 ppm ( C). These
spectroscopic investigations led to the assignment of 1 as a
distorted trigonal bipyramidal compound, which was unambig-
uously confirmed via a single-crystal X-ray diffraction study
(Figure 2). Compound 1 crystallized with two molecules in the
Figure 3. Crystal packing of the solid-state structure of 2 presented
with 50% probability ellipsoids. Hydrogen atoms have been removed
for clarity, except for N−H and the formyl hydrogen atoms.
Complex 2 crystallized as an intermolecularly hydrogen
bound dimer. The hydrogen bond is formed between the
formate carbonyl oxygen and the N−H proton of a neighboring
molecule (see Figure 3), with a hydrogen bond distance of
Figure 2. One of the two molecules present in the asymmetric unit cell
of the solid-state structure of 1 shown with 50% probability ellipsoids.
Hydrogen atoms have been removed for clarity.
2
.207 Å. The Mn−phosphorus distance lengthens to 2.300(1)
Å from 2.256(1) Å in 1, while the Mn−N distance lengthens to
2
.107(1) Å from 1.882(1) Å observed in 1.
Nature has employed manganese in the active site of several
metalloenzymes for the decomposition of oxalic acid (OA).
asymmetric unit. The nitrogen of the ligand adopts a trigonal
planar geometry (average sum of the angles about N =
13
Piacenti demonstrated the decarboxylation of OA in the
laboratory using homogeneous ruthenium hydride carbonyl
3
58.2(2)°) attributed to a high degree of lone pair donation
12
into the metal center. This strong bonding is demonstrated
14
clusters. The ability to mimic this reactivity with a molecular
manganese complex theoretically yields 50% more gas per mole
of OA as compared to FA. For the purpose of generating PV-
work rather than hydrogen storage, OA is a more desirable
substrate. For this reason we also sought to explore the
reactivity of 1 with oxalic acid. A dilute THF solution of 0.5
equiv of OA was added to a hexane solution of 1, and the red
color immediately turned yellow (Scheme 3).
by the short Mn(1)−N(1) bond distance of 1.882(1) Å
(
average of the two distances from the two molecules present
iPr
H
in the asymmetric unit cell) as compared to ( PN P)Mn-
1
0
(
CO) Br (2.116(4) Å). The phosphorus−metal bond lengths
2
of 1 are contracted to 2.256(1) Å from 2.297(1) Å found in the
starting bromide complex. The IR stretches of the carbonyl
−1
resonances in 1, 1817 and 1894 cm , are also lower in energy
−1
than the starting bromide complex (1824 and 1916 cm ) and
iPr
are comparable to the analogous iron complex ( PNP)Fe-
−
1
9b
Scheme 3. Summary of 1,2-Addition of OA to 1 to Yield 3
with Isolated Yield
(
CO)(H) (1862 cm ).
Compound 1 is able to undergo 1,2-addition with formic acid
(
Scheme 2), the first step in the previously proposed catalytic
9b
cycle of FA decomposition. Adding a dilute THF solution of
FA to a red solution of 1 in hexane elicits an immediate color
change to yellow, concurrent with a precipitation of a yellow
13
1
powder. NMR ( C and H) analysis of the precipitate reveals a
top/bottom inequivalent complex with four isopropyl methyl
resonances, a formyl proton at 9.00 ppm, and the N−H proton
1
13
at 8.18 ppm ( H NMR). The C NMR spectrum contained
B
DOI: 10.1021/acs.organomet.6b00274
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Communication
The yellow precipitate that formed was isolated and analyzed.
The 13C NMR spectrum contained resonances for the pair of
carbonyl ligands (231.6 and 229.3 ppm), and their IR stretching
frequencies are 1913 and 1821 cm . The H NMR spectrum
was very similar to that of 2, with four methyl resonances from
the isopropyl methyl groups and the resonance for the N−H
proton found at 8.35 ppm. These data are consistent with the
Our initial results have been focused on either varying the
catalyst loading and keeping the concentration of FA constant
or varying the concentration of FA and keeping the
concentration of catalyst constant. For each run we evaluated
the total pressure generated and compared it to the theoretical
−1
1
pressure yield of H and CO (see SI for details). The catalytic
2 2
turnover of these systems was generally several orders of
magnitude less than those obtained from the known iron
1
,2-addition product of OA over two manganese centers to give
iPr
H
system. The gas generated in the LiBF -free runs typically
the oxalate-bridged complex {( PN P)Mn(CO) } (μ-
4
2
2
stopped generating pressure just under 50% of the theoretical
pressure. With a higher catalyst loading, 56% of the theoretical
pressure was achieved. Analysis of the reaction mixtures as well
as the generated gases revealed the presence of H and CO as
O CCO ) (3). The proton NMR shift of the N−H proton is
2
2
an indicator of the strength of the hydrogen bonding, with
15
further downfield shifts indicating stronger interactions. The
similarity in the N−H shift in compounds 2 and 3 indicates
similar hydrogen-bonding interactions in solution. From this we
propose that 2 is monomeric in solution and dimerizes upon
crystallization. A solid-state structure was obtained to
unambiguously assign the structure of 3.
2
2
expected, but also large quantities of water. This indicates that
not only is the dehydrogenation pathway active, but a
dehydration pathway is also present under catalytic conditions,
which would also produce an equivalent of CO. As we failed to
13
find CO in the C NMR spectrum, CO was detected by
Complex 3 crystallized as the desired oxalate-bridged
bimetallic compound. The hydrogen bond lengths between
the oxalate carbonyl and their respective hydrogen bond donor
N−H are 1.988 and 1.864 Å, both significantly shorter than the
intermolecular hydrogen bond (2.207(5) Å) of 2. Similar to 2,
the Mn(1)−phosphorus distances lengthen to 2.299(1) and
iPr
carbonylating ( PONOP)Fe(Cl) with the gas generated from
2
one of the catalytic runs to yield the known complex
i P r
i P r
(
(
PONOP)Fe(Cl) (CO) ( PONOP = 2,6-bis-
2
16
diisopropylphosphinito)pyridine). This result could explain
the low yields of pressure, as either CO or water may poison
the catalyst.
2.284(1) Å in 3 from 2.256(1) Å in 1, and the Mn(1)−N(1)
Surprisingly, addition of a Lewis acid, LiBF , has an
4
distances lengthen to 2.129(2) and 2.114(2) Å, respectively. A
table comparing select spectral and structural parameters can be
found in the SI. With the successful synthesis and character-
ization of the 1,2-addition products in hand, we moved to
investigate these compounds’ competency for decarboxylation
catalysis.
inhibitory effect on the catalysis. The reactions performed in
the presence of 3 or 6 mol % LiBF would only slowly generate
4
gas and resulted in 13% or 19% of the theoretical pressure,
respectively. Employing the same reaction conditions without
the Lewis acid resulted in 48% of the expected pressure. This
result is in stark contrast to the previously reported iron
systems, where a Lewis acid is all but necessary to observe
catalytic turnover. It is unknown at this time which of the two
pathways, dehydrogenation or dehydration, the LiBF4 is
disturbing. We continue to work to deconvolute the
mechanisms at play with formic acid decomposition that is
catalyzed by 2.
The decomposition of FA was performed with the use of 2 in
9b
a 1,4-dioxane solution, using a previous protocol as a model.
Initially we tried using a highly concentrated FA solution (∼5
M) with low catalyst (<0.1%) loadings and a Lewis acid and
were met with no catalytic activity. We suspect, from the whole
of our study, that the manganese catalyst is not robust under
these catalytic conditions and degrades faster than turnover
with such a high concentration of FA. Moving to a much more
dilute acid concentration (<1.5 M) and a higher catalyst loading
of roughly 1 mol % resulted in the catalytic turnover of FA with
Although the decomposition of FA proved to be more
complicated than desired, catalysis using OA was nonetheless
attempted. Under comparable conditions employing OA in 1,4-
dioxane, no catalytic turnover was observed. Under all
conditions attempted, only slight increases of pressure were
observed when attempting OA decarboxylation, which we
attribute to catalyst decomposition. However, our work with
OA is ongoing, including the use of exogenous oxidizing agents.
This report is an example of the ability of Mn(I) to affect the
decomposition of FA. Although the results indicate a more
complicated mechanism than that proposed for the analogous
2
(Table 1). The turnover was calculated based on total
pressure generated versus the expected pressure from
generating H and CO from FA.
2
2
Table 1. Summary of the Catalytic Results of 2 with FA in a
Dioxane Solution
PSI, 1 h (%
PSI, 14 h (%
mol % 2,
9b
a
b
b
c
Fe(II) system, we will continue to pursue this reaction and
attempt to clarify the competing product formation. These
initial results focus on exploring the conditions under which 2
can affect catalytic turnover. Full kinetic analysis of the reaction
may allow us to deconvolute the differing reaction pathways
observed using 2 as a catalyst for FA decomposition. The Lewis
acid inhibition warrants further examination, as the Lewis acid
is integral to the catalytic activity of the iron system. Ongoing
studies aim to clarify the inhibition by a Lewis acid in the
system.
catalyst system
yield)
yield)
TON
[
[
[
[
[
[
0.005] 2, [0.435] FA
0.005] 2, [0.870] FA
0.005] 2, [1.305] FA
0.002] 2, [0.870] FA
0.008] 2, [0.870] FA
9.1, 36%
10.3, 21%
13.8, 18%
2.8, 5%
12.0, 48%
23.8, 48%
36.1, 48%
18.9, 38%
28.4, 57%
9.5, 19%
1.3%, 37
0.6%, 74
0.4%, 111
0.3%, 190
1.3%, 60
0.6%, 19
13.1, 26%
2.6, 5%
0.005] 2, [0.870] FA, 3%
b
LiBF4
[
0.005] 2, [0.870] FA, 6%
2.6, 5%
6.6, 13%
0.6%, 13
b
LiBF4
a
The initial molarity of catalyst and formic acid of the reaction
SUMMARY AND CONCLUSION
This work describes the synthesis of a 16 e manganese
dicarbonyl complex that undergoes facile 1,2-addition of both
formic and oxalic acids. This reactivity is analogous to the
b
■
solution in 5 mL of dioxane. Total pressure expected for varying FA
−
amounts is given in the SI; percentages assume FA conversion to H
2
c
and CO . Turnover number at 14 h for the given mol % of catalyst
2
used.
C
DOI: 10.1021/acs.organomet.6b00274
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Communication
isoelectronic (PNP)Fe(H)(CO) previously described in the
literature. The formate complex 2 proved competent for FA
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H
use of (PN P)Fe(O CH)(H)(CO), 2 is active for both
2
dehydration and dehydrogenation of FA. We postulate that
the dehydration pathway is responsible for the low turnover
observed in the catalysis. The addition of Lewis acid to the
reaction mixtures further inhibited catalysis. Attempts to
decarboxylate OA were unsuccessful. This preliminary report
of manganese-mediated FA decomposition catalysis shows
pressure generation too low for our requirements, as well as
generating CO, which makes this particular compound
unsuitable for fuel cell work, but represents the first observation
that manganese can decompose formic acid into H and CO .
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ASSOCIATED CONTENT
Supporting Information
■
*
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.6b00274.
(8) (a) Bertoli, M.; Choualeb, A.; Lough, A. J.; Moore, B.; Spasyuk,
D.; Gusev, D. G. Organometallics 2011, 30, 3479−3482. (b) Alberico,
E.; Sponholz, P.; Cordes, C.; Nielsen, M.; Drexler, H.-J.; Baumann, W.;
Junge, H.; Beller, M. Angew. Chem., Int. Ed. 2013, 52, 14162−14166.
(c) Nielsen, M.; Alberico, E.; Baumann, W.; Drexler, H. J.; Junge, H.;
Gladiali, S.; Beller, M. Nature 2013, 495, 85−89.
Experimental details, spectra, crystallographic tables, and
a more detailed description of the catalysis (PDF)
Crystallographic data for 1, 2, and 3 (CIF)
(
9) (a) Bielinski, E. A.; Fo
Hazari, N.; Holthausen, M. C. ACS Catal. 2015, 5, 2404−2415.
b) Bielinski, E. A.; Lagaditis, P. O.; Zhang, Y.; Mercado, B. Q.;
̈
rster, M.; Zhang, Y.; Bernskoetter, W. H.;
AUTHOR INFORMATION
Corresponding Author
E-mail (J. M. Boncella): boncella@lanl.gov.
■
(
*
Wurtele, C.; Bernskoetter, W. H.; Hazari, N.; Schneider, S. J. Am.
Chem. Soc. 2014, 136, 10234−10237. (c) Koehne, I.; Schmeier, T. J.;
Bielinski, E. A.; Pan, C. J.; Lagaditis, P. O.; Bernskoetter, W. H.;
Takase, M. K.; Wurtele, C.; Hazari, N.; Schneider, S. Inorg. Chem.
Notes
The authors declare no competing financial interest.
2
̈
014, 53, 2133−2143. (d) Chakraborty, S.; Lagaditis, P. O.; Forster,
ACKNOWLEDGMENTS
■
M.; Bielinski, E. A.; Hazari, N.; Holthausen, M. C.; Jones, W. D.;
Schneider, S. ACS Catal. 2014, 4, 3994−4003.
(10) Tondreau, A. M.; Boncella, J. M. Polyhedron 2016,
DOI: 10.1016/j.poly.2016.04.007.
A.M.T. acknowledges a Director’s funded postdoctoral fellow-
ship from Los Alamos National Laboratory for support. We
also wish to acknowledge LANL Science Campaign 5 for partial
support of this research.
(
11) (a) Radosevich, A. T.; Melnick, J. G.; Stoian, S. A.; Bacciu, D.;
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Chem. 2009, 48, 9214−9221. (b) Bacciu, D.; Chen, C. H.;
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D
DOI: 10.1021/acs.organomet.6b00274
Organometallics XXXX, XXX, XXX−XXX