Formation of N, N-Dimethylacrylamide by a Multicenter Hydrocarbamoylation of C2H2 with N, N-Dimethylformamide Activated by Ru5(μ5-C)(CO)15

Article abstract of DOI:10.1021/acs.inorgchem.8b00460

Hydrocarbamoylation of C₂H₂ by N,N-dimethylformamide (DMF) to N,N-dimethylacrylamide was effected by a series of cluster-opening reactions with Ru₅(μ₅-C)(CO)₁₅ (1). The reaction of 1 with DMF yielded the new complexes Ru₅(μ₅-C)(CO)₁₄(μ-n²-O=CNMe₂)(μ-H) (2) and a minor coproduct Ru₅(μ₅-C)(CO)₁₃(HNMe₂)(μ-n²-O=CNMe₂)(μ-H) (3) by a cluster-opening activation of the formyl C-H bond of DMF. Compound 3 was obtained from 2 by a further reaction with DMF. Compound 3 reacted with C₂H₂ (1 atm, 70 °C) to yield Ru₅(μ₅-C)(CO)₁₃(μ-n³-O=CNMe₂CHCH)(μ-H) (4) by the addition and coupling of C₂H₂ to the bridging dimethylformamido ligand. Compound 4 contains a σ-π-coordinated, dimethylformamido-substituted vinyl ligand that bridges a Ru-Ru edge of an open Ru₅C cluster. The formamido group is also coordinated to one of the metal atoms. The addition of CO (1 atm, 25 °C) to 4 yielded the CO adduct Ru₅(μ₅-C)(CO)₁₄(n²-O=CNMe₂CH=CH)(μ-H) (5) containing a chelating dimethylacrylamido ligand, which released dimethylacrylamide by the reductive elimination of a C-H bond upon a further addition of CO (400 psi, 125 °C) with the re-formation of 1. All of the products were characterized by single-crystal X-ray diffraction analyses.

Full text of DOI:10.1021/acs.inorgchem.8b00460

Communication
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Formation of N,N‑Dimethylacrylamide by a Multicenter
Hydrocarbamoylation of C2H2 with N,N‑Dimethylformamide
Activated by Ru5(μ5‑C)(CO)15
Richard D. Adams* and Jonathan D. Tedder
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29028, United States
S
* Supporting Information
ABSTRACT: Hydrocarbamoylation of C2H2 by N,N-
dimethylformamide (DMF) to N,N-dimethylacrylamide
was effected by a series of cluster-opening reactions with
Ru5(μ5-C)(CO)15 (1). The reaction of 1 with DMF
yielded the new complexes Ru5(μ5-C)(CO)14(μ-η2-O
CNMe2)(μ-H) (2) and a minor coproduct Ru5(μ5-
C)(CO)13(HNMe2)(μ-η2-OCNMe2)(μ-H) (3) by a
cluster-opening activation of the formyl C−H bond of
DMF. Compound 3 was obtained from 2 by a further
reaction with DMF. Compound 3 reacted with C2H2 (1
atm, 70 °C) to yield Ru5(μ5-C)(CO)13(μ-η3-O
CNMe2CHCH)(μ-H) (4) by the addition and coupling
of C2H2 to the bridging dimethylformamido ligand.
Scheme 1. Reaction and Interconversions of Re2(CO)8[μ-η2-
Compound 4 contains a σ−π-coordinated, dimethylforma-
C(H)C(H)Bun](μ-H) with DMF
mido-substituted vinyl ligand that bridges a Ru−Ru edge
of an open Ru5C cluster. The formamido group is also
coordinated to one of the metal atoms. The addition of
CO (1 atm, 25 °C) to 4 yielded the CO adduct Ru5(μ5-
C)(CO)14(η2-OCNMe2CHCH)(μ-H) (5) contain-
ing a chelating dimethylacrylamido ligand, which released
dimethylacrylamide by the reductive elimination of a C−H
bond upon a further addition of CO (400 psi, 125 °C)
with the re-formation of 1. All of the products were
esterifications6 (eq 3), and even hydrocarbamoylations7 (eq
characterized by single-crystal X-ray diffraction analyses.
4) of olefins and alkynes by metal complexes have been effected
by the activation of formyl C−H bonds, but mechanistic details
are rarely provided.
crylamides, like other acryloyl compounds, are precursors
1
In recent studies, we have found that the dinuclear rhenium
Ato a range of valuable polymers. As a result, the syntheses
complex Re2(CO)8[μ-η2-C(H)C(H)Bun](μ-H) reacts with
of these acryloyl compounds have received considerable
attention.2 We have now found that N,N-dimethylacrylamide
DMF by the elimination of 1-hexene and activation of the
formyl C−H bond to yield the complexes Re2(CO)8(μ-η2-O
(DMA) can be obtained by the hydrocarbamoylation of C2H2
CNMe2)(μ-H) and Re2(CO)7(NHMe2)(μ-η2-OCNMe2)(μ-
H), both of which contain a bridging N,N-dimethylformamido
ligand (see Scheme 1).8
We have now found that the pentaruthenium carbonyl
complex9 1 reacts with DMF by activation of the formyl C−H
bond to yield the new dimethylformamido complex Ru5(μ5-
C)(CO)14(μ-η2-OCNMe2)(μ-H) (2; 64% yield) together
with a minor, but important coproduct Ru5(μ5-C)-
by N,N-dimethylformamide (DMF; eq 1) in a series of
(CO)13(HNMe2)(μ-η2-OCNMe2)(μ-H) (3; 3% yield).
reactions facilitated by a combination of the activation of the
Compounds 2 and 3 were also obtained independently, albeit
formyl C−H bond of DMF and the addition of C2H2 to the
in low yields 12% and 14%, respectively, from the reaction of 1
cluster complex Ru5(μ5-C)(CO)15 (1).
with NHMe2. Compound 3 was also obtained from 2 (71%
While the activation and functionalization of C−H bonds by
metal atoms have received much attention in recent years, most
studies have been focused on the activation of aliphatic3 and
Received: February 21, 2018
aromatic4 C−H bonds. Hydroacylations5 (eq 2), hydro-
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.8b00460
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Inorganic Chemistry
Communication
Figure 3. ORTEP diagram of the molecular structure of 4 showing
25% thermal ellipsoid probability. The methyl hydrogen atoms have
been omitted for clarity. Selected interatomic bond distances (Å) are
as follows: Ru1−Ru3 = 2.9491(5), Ru1−Ru5 = 2.8531(5), Ru1−Ru2
= 2.8248(5), Ru2−Ru5 = 2.8986(5), Ru2−Ru3 = 2.8409(5), Ru3−
Ru4 = 2.7279(5), Ru4−Ru5 = 3.0092(5), Ru1−H1 = 1.70(6), Ru2−
H1 = 1.60(6), Ru4−C3 = 2.013(4), Ru4−O1 = 2.114(2), Ru3−C2 =
2.262(4), Ru3−C3 = 2.186(4), C1−O1 = 1.264(5).
Figure 1. ORTEP diagram of the molecular structure of 2 showing
15% thermal ellipsoid probability. Selected interatomic bond distances
(Å) are as follows: Ru1−Ru3 = 2.8349(6), Ru1−Ru5 = 2.8265(5),
Ru1−Ru2 = 2.8890(5), Ru2−Ru5 = 2.8588(5), Ru2−Ru3 =
2.8606(6), Ru3−Ru4 = 2.8690(5), Ru4−Ru5 = 2.8760(5), Ru1−H1
= 1.79(5), Ru2−H1 = 1.80(5), Ru1−C1 = 2.067(4), Ru4−O1 =
2.100(3), C1−O1 = 1.280(5).
Figure 4. ORTEP diagram of the molecular structure of 5 showing
20% thermal ellipsoid probability. Methyl hydrogen atoms have been
omitted for clarity. Selected interatomic bond distances (Å) are as
follows: Ru1−Ru3 = 2.8437(5), Ru1−Ru5 = 2.8301(5), Ru1−Ru2 =
2.8458(5), Ru2−Ru5 = 2.8471(5) Ru2−Ru3 = 2.8706(5), Ru3−Ru4 =
2.9501(5), Ru4−Ru5 = 2.9549(5), Ru1−H1 = 1.66(4), Ru2−H1 =
1.79(4), Ru4−C3 = 2.034(5), Ru4−O1 = 2.155(3), C1−O1 =
1.282(5), C1−C2 = 1.452(7), C2−C3 = 1.330(8).
Figure 2. ORTEP diagram of the molecular structure of 3 showing
20% thermal ellipsoid probability. Selected interatomic bond distances
(Å) are as follows: Ru1−Ru3 = 2.8087(11), Ru1−Ru5 = 2.8184(11),
Ru1−Ru2 = 2.8950(11), Ru2−Ru5 = 2.8544(11), Ru2−Ru3 =
2.8541(12), Ru3−Ru4 = 2.8776(12), Ru4−Ru5 = 2.9049(12), Ru1−
H1 = 1.77(8), Ru2−H1 = 1.82(8), Ru4−N2 = 2.201(11), Ru1−C1 =
2.072(10), Ru4−O1 = 2.090(7), C1−O1 = 1.299(12).
yield) by the reaction with an additional quantity of DMF at 98
°C for 8 h and by a direct reaction of 2 with NHMe2. The
NHMe2 ligand was presumably formed by decarbonylation of
DMF in the first reaction. Other metal complexes have been
shown to decarbonylate DMF via pathways that involve an
initial activation of the formyl C−H bond.10 Both compounds
dimethylformamido ligand formed by cleavage of the formyl
C−H bond of DMF and its addition to the Ru5 cluster. One
Ru−Ru bond in the cluster was cleaved by the addition and the
μ-η2-OC-dimethylformamido ligand that bridges the opened
edge of the Ru5 cluster. In combination, the bridging
formamido and hydrido ligands in 2 formally donate four
electrons to the metal atoms, but 1 loses only one CO ligand
(two electrons) in the formation of 2. Thus, the opening of the
cluster by the cleavage of one of the Ru−Ru bonds plays a key
role in the success of the reaction by providing the equivalent of
another “vacant” coordination site for the two additional
electrons. In addition, the carbido carbon atom C0 plays an
1
were characterized by IR, H NMR, mass spectrometry, and
single-crystal X-ray diffraction analyses. ORTEP diagrams of the
molecular structures of 2 and 3 are shown in Figures 1 and 2,
respectively. Both compounds contain a hydrido ligand that
bridges the Ru1−Ru2 bond, δ −21.47 and δ −21.99, in the 1H
NMR spectra of 2 and 3, respectively, and a bridging
B
DOI: 10.1021/acs.inorgchem.8b00460
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Inorganic Chemistry
Communication
The sequence of transformations is overall tantamount to the
hydrocarbamoylation of C2H2 by DMF (eq 1). Although
regeneration of 1 in the final step formally closes what could be
considered to be a “catalytic” cycle (Scheme 2), the reaction is
not yet effectively catalytic because of certain low yield
transformations, such as 3 to 4, and the use of CO, which
effectively inhibits the second loop through the cycle that
requires additional reactions with DMF.
Scheme 2. Schematic of the Hydrocarbamoylation of C2H2
with DMF by 1
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.8b00460.
Synthetic details and NMR spectroscopic data along with
structural characterizations of the new compounds
(PDF)
Accession Codes
CCDC 1824915−1824918 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by email-
ing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Author
*E-mail: adamsrd@mailbox.sc.edu.
ORCID
important role by holding the cluster together. Compound 3
contains an NHMe2 ligand on one of the metal atoms, Ru4, in
place of one of the terminal CO ligands in 2 [Ru4−N2 =
2.201(11) Å].
■
Most interestingly, complex 3 was found to react with C2H2
under a slow purge (1 atm) at 70 °C for 5 h to yield the new
complex Ru5(μ5-C)(CO)13[μ-η3-OCN(Me)2CHCH](μ-H)
(4; 6% yield). Compound 4 was characterized crystallo-
graphically, and an ORTEP diagram if its molecular structure
is shown in Figure 3. Compound 4 contains a dimethylforma-
mido-substituted, σ−π-vinyl ligand that bridges the Ru3−Ru4
edge of the open Ru5C cluster by the carbon atoms C2 and C3
[Ru3−C2 = 2.262(4) Å, Ru3−C3 = 2.186(4) Å, and Ru4−C3
= 2.013(4) Å]. The formamido group is coordinated to Ru4 by
its oxygen atom O1 [Ru4−O1 = 2.114(2) Å]. This unusual
ligand was formed from displacement of the labile NHMe2
ligand from 3 followed by the addition and C−C coupling of
C2H2 to the carbon end of the bridging formamido ligand.
Interestingly, we have not been able to obtain 4 from 2 by
reaction with C2H2. Presumably, this is because C2H2 is not
able to displace the more strongly coordinated CO ligands on
2.
Richard D. Adams: 0000-0003-2596-5100
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This research was supported by Grant CHE-1464596 from the
National Science Foundation to R.D.A. The authors thank Dr.
Mark Smith for providing the X-ray diffraction data for
compound 2.
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