Journal of Molecular Structure 1296 (2024) 136868

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstr

Carboxylative cyclization of propargyl alcohols with carbon dioxide for the

synthesis of α-alkylidene cyclic carbonates in presence of Co(III) schiff base
complex catalyst
Juli Nanda Goswami a, Najirul Haque b, Asiful H. Seikh c, Biswajit Bhattacharya d,
Franziska Emmerling d, Nimai Bar e, Ahmad A. Ifseisi f, Surajit Biswas b, *, Malay Dolai a, *
a
Department of Chemistry, Prabhat Kumar College, Purba Medinipur 721404, West Bengal, India
b
Department of Chemistry, University of Kalyani, Kalyani, Nadia 741235, West Bengal, India
c
Mechanical Engineering Department, College of Engineering, King Saud University, Riyadh 11421, Saudi Arabia
d
BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Str, Berlin 11 12489, Germany
e
Raja Narendralal Khan Women’s College (Autonomous), Paschim Medinipur, West Bengal 721102, India
f
Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords:
Cobalt (III) Schiff base complex
X-ray crystal analysis
Catalytic fixation of carbon dioxide
Carboxylative cyclization of propargyl alcohols
А-alkylidene cyclic carbonates
DFT calculations
A cobalt(III) complex, [Co(L)3](DMF) (1) of Schiff base ligand HL, 2-((E)-(benzylimino)methyl)-4-bromophenol
is prepared and single crystal X-ray structural analysis have also been performed. The structures of complex 1
showed hexa-coordinated mononuclear systems that adopt octahedral geometry. The complex has also exhibited
the supramolecular networks through non-covalent interactions like H-bonding, C–Hπ stacking. Moreover, the
complex 1 is very effective in the catalytic fixation of carbon dioxide in propergyl alcohols to produce α-alky­
lidene cyclic carbonates. The catalytic production of α-alkylidene cyclic carbonates have been carried out
through carboxylative cyclization of propargyl alcohols using CO2 balloon of 1 atm pressure at 80 ◦ C. Solvent
free condition (green synthesis) made this catalytic protocol eco-friendly towards the environment. Utilizing
various substrates of propargyl alcohols moderate to high percentage yield (62–95%) of respective α-alkylidene
cyclic carbonates product have been isolated over this catalytic reaction. Besides, the theoretical calculations
(DFT) was performed for the prediction of probable mechanism of the catalytic reaction.

1. Introduction pivotal role towards a clean environment [3–7]. Again, CO2 is

Realistic resource management is the most important feasible
development for the future generation. The present stage of sustain­
ability is silently required enormous advancement as it is outlying far
from the satisfactory point. Till date coal, crude oil and natural gas are
the prime resources of carbon. Thus carbon dioxide along with biomass
can be an additional appropriate alternative for the renewable carbon
assets. Due to the fulfillment of global energy requirement a substantial
quantity of carbon dioxide has been released from combustion of fossil
fuels after the industrial revolution. CO2 is the principal constituent of
greenhouse gasses, producing global warming which causes drastic
change of the climate [1,2]. As a result it is very urgent to reduce CO2
emission into the atmosphere by the means of storage or usages. Recy­
cling and reduction of CO2 into valuable fine chemicals can play a
economical, ecological and most abundant C1-resourses as a result
exploitation of it in chemical fixation is gaining ample attention
currently [8–11]. Chemical fixation of carbon dioxide in order to pro­
duce valuable fine chemicals under mild reaction conditions is chal­
lenging due to kinetic and thermodynamic stability of carbon dioxide. In
this regards design, synthesis and utilization of suitable catalyst is very
much essential for the fixation of thermodynamically and kinetically
stable CO2 [12–16].
Numerous catalytic protocols has been developed for the fixation of
carbon dioxide to produce cyclic carbonates [17–19], α-alkylidene cy­
clic carbonates [20–22] are organic carbamates [23–26], oxazolidinones
[27,28], benzimidazoles [29–31], quinazolidinone [32–34], N-methyl­
ated [35] and N-formylated products [36] etc. Among the before
mentioned CO2 fixation products, α-alkylidene cyclic carbonates is one

* Corresponding authors.
E-mail addresses: surajit.jrf@gmail.com (S. Biswas), dolaimalay@yahoo.in (M. Dolai).

https://doi.org/10.1016/j.molstruc.2023.136868
Received 26 July 2023; Received in revised form 23 September 2023; Accepted 16 October 2023
Available online 20 October 2023
0022-2860/© 2023 Elsevier B.V. All rights reserved.
J.N. Goswami et al.
Scheme 1. The schematic presentation of the formation of ligand HL.
Scheme 2. Schematic diagram for synthesis of 1.
of the most important class of organic compounds. This compound are
commonly found in pharmaceuticals, agrochemicals and natural prod­
ucts such as Cycloolivil carbonate, Genkwanin I, Guaianolide
holo-leucin, etc. [37–39]. In addition, they are very useful reagents for a
variety of organic transformations [40–43]. Synthesis of α-alkylidene
cyclic carbonates by carboxylative cyclization of propargyl alcohols via
catalytic carbon dioxide fixation reaction is eco-friendly and promising
pathway developed recently. Several catalytic systems such as phos­
phines [44], azole-anion-based aprotic ionic liquids [45], bicyclic gua­
nidines [46], N-heterocyclic carbene/carbon dioxide adducts [47],
N-heterocyclic olefin/carbon dioxide adducts [48],
alkoxide-functionalized imidazolium betaines/carbon dioxide adducts
[49] etc. were used as metal free catalyst for this purpose. Besides, some
metal-based catalysts like copper [50–53], cobalt [54], palladium [55],
zinc [56], tungsten [57], ruthenium [58], and silver [59–63] also been
utilized for the same compound synthesis. However, most of the re­
ported methods required either high pressure of carbon dioxide or
drastic reaction conditions. Recently, S. M. Islam and his group pub­
lished a paper where silver nanoparticles embedded COF catalyst pro­
duced α-alkylidene cyclic carbonates through carboxylative cyclization
of propargyl alcohols under mild reaction conditions [64].
Despite some advancement in this catalytic field, only one report has
been published earlier where cobalt metal-based catalyst is used for the
production of α-alkylidene cyclic carbonates [54]. Cobalt is relatively
low cost first row transition metal. In this article, a Schiff base ligand HL,
2-((E)-(benzylimino)methyl)− 4-bromophenol was used for the synthe­
sis of mononuclear robust cobalt(III) complex [Co(L)3](DMF) (1) which
was effective as catalyst for fixation of carbon dioxide to synthesize
α-alkylidene cyclic carbonates through carboxylative cyclization of
propargyl alcohols under mild condition. The complex 1 showed
excellent catalytic activity with high selectivity. Moreover, theoretical
calculations have performed to establish the probable mechanistic
pathway of the catalytic reaction.
2. Experimental section
2.1. Synthesis of the ligand (HL)
The ligand HL, was prepared by the Schiff base condensation reac­
tion following the procedure of previous report (Scheme 1) [65]. Anal.
Calc. for C14H12BrNO (MW 290.15): Calc. C, 57.95; H, 4.17; N, 4.83;
Found: C, 57.91; H, 4.15; N, 4.88%.1HNMR (400 MHz, DMSO) (Fig.-S1)
2
Journal of Molecular Structure 1296 (2024) 136868
δ 13.56 (s, 1H), 8.71 (s, 1H), 7.72 (d, J = 2.5 Hz, 1H), 7.48 (dd, J = 8.8,
2.5 Hz, 1H), 7.43–7.27 (m, 5H), 6.87 (d, J = 8.8 Hz, 1H), 4.82 (s, 2H). IR
(KBr, cm− 1): 1621 (s), 1498 (s), 1267 (s), 1131 (s) (Fig. S2).
2.2. Synthesis of complex 1
Complex 1 is prepared by mixing CoCl2⋅6H2O (0.047 g, 0.2 mmol)
and HL (0.0656 g, 0.2 mmol) in a mixture solution of acetonitrile/DMF
(v/v = 15/5 mL). Then the triethylamine (0.0202 g, 0.2 mmol) was
added and the mixture was continued to stir for 45 minutes more to give
dark brown solution (Scheme 2). The solution has been left untouched
for slow evaporation after filtration. The dark brown single crystals,
suitable for single crystal X-ray diffraction obtained in few days. Then
crystals were washed through cold MeCN and sent to SCXRD instrument.
Anal.Calc. for C45H40Br3CoN4O4 Yield:0.519 g. (52%) (MW 999.47): C,
54.08; H, 4.03; N, 5.61. Found: C, 54.05; H, 4.02; N, 5.59%. 1HNMR
(400 MHz, DMSO) ( Fig.S3). IR (KBr, cm− 1): 3475(b), 1619 (s), 1493 (s),
1265 (s), 1130 (s) (Fig. S4).
2.3. Catalytic procedure for the synthesis of α-alkylidene cyclic carbonate
from propargyl alcohols
Propargyl alcohol (8 mmol), DBU (Diazabicyclo(5.4.0)undec‑7-ene)
(8 mmol) and catalyst (0.005 mmol) were taken in a 25 ml rb flask. Then
CO2 (99.99%) balloon was connected with the flask and it was vac­
uumed and purged with carbon dioxide three times to remove air from
the reaction vessel. The mixture was stirred at 80 ◦ C under oil bath. The
progress of reaction was monitored by TLC (thin layer chromatography)
technique. After completion of reaction, the mixture was filtered and
concentrated through rota-evaporator. The obtained crude product was
purified through column chromatography on silica gel using ethyl ace­
tate and petroleum ether mixture as eluent. The pure product was
characterized by NMR (1H and 13C) spectroscopy.
3. Result and discussion
3.1. Crystal structure description for [Co(L)3].DMF(1)
The single crystal X-ray diffraction studies reveal that the complex 1
is mononuclear cobalt(III) complexes where the central atom is bounded
by three bidentate NO donor Schiff base ligand (HL).
The complex 1 ([CoIII (L)3].DMF) crystallized in the monoclinic
J.N. Goswami et al. Journal of Molecular Structure 1296 (2024) 136868

combination of two C–H…π bonds C40-H40…Cg1(ring C29, C30, C31,

C32, C33, C34) and C11-H11…Cg1(ring C29, C30, C31, C32, C33, C34)
distance of 2.83 Å leads to the formation of supramolecular 1D chain
running along the crystallographic c axis. The third C–H…π bond C27-
H27…Cg2(ring C15, C16, C17, C18, C19, C20) distance of 2.79 Å sup­
ports the formation of 2D supramolecular layer parallel with the crys­
tallographic ac plane.

3.2. UV–Vis spectra for complex [Co(L)3].DMF(1)

Electronic spectra of complex 1 is shown in Fig. 3, were recorded in

MeCN (4 × 10− 5 (M)) solution. The first two peaks are at 226 nm and

Fig. 1. The ORTEP view of complex 1 (C atoms not lebelled for clarity). DMF
molecule is also omitted for clarity.

crystal system with space group P21/n. It is observed that the geometry
of 1 is octahedral where Co1 is hexa-coordinated by three deprotonated
HL ligands (namely N1, O1, N2, O2 and N3, O3). The DMF as solvent
molecule is situated in the unit cell of 1 (Fig. 1). The crystal data and
details of the structure determination for 1 are given in Table S1. The Co-
Oi bond lengths lie in the span of 1.888–1.893 Å as well as the Co-Ni
bond lengths lie in the range of 1.929–1.948 Å for 1. The certain bond
distances and angles for complex 1 are tabulated in Table S2 and S3.
The molecules of complex 1 connected by C40-H40…Cg1(ring C29,
C30, C31, C32, C33, C34) interaction with H40…Cg1(ring C29, C30,
C31, C32, C33, C34) distance of 2.856 Å generate supramolecular 1D
chain extending nearly parallel with [− 101] direction (Fig. 2). However, Fig. 3. Electronic spectra of [CoIII(L)].DMF in acetonitrile.

Fig. 2. The molecular view of (a) 1D network through CH… π interactions (green dotted line) extending nearly parallel with [− 101] direction and (b) 2D network
through CH… π interactions (skyish blue dotted line) in the crystallographic ac plane in complex 1.

3
J.N. Goswami et al. Journal of Molecular Structure 1296 (2024) 136868

Scheme 3. Catalytic carboxylative cyclization of propargyl alcohols in pres­
ence of carbon dioxide for the synthesis of α-alkylidene cyclic carbonates.
253 nm is due to intra-ligand charge transfer transitions (ILCT). The
band at 401 nm in the electronic spectrum is due to ligand to metal
charge transfer transition (LMCT) which is indication of the metal
complex formation.
3.3. Catalytic synthesis of α-alkylidene cyclic carbonates through
carboxylative cyclization of propargyl alcohols
The catalytic activity of the synthesized robust cobalt (III) complex
(1) have been checked in the production of α-alkylidene cyclic carbon­
ates through carboxylative cyclization of propargyl alcohols with carbon
dioxide (Scheme 3). First of all a variety of control experiments were
carried out to identify the optimized catalytic reaction conditions using
2-methyl-3-butyn-2-ol as model propargyl alcohol under 1 atm CO2
pressure. Initial experiment was done by taking 2-methyl-3-butyn-2-ol
(8 mmol), 1,8-diazabicyclo(5.4.0)undec‑7-ene (DBU) (8 mmol), in ab­
sent of any catalyst at 60 ◦ C under neat and homogeneous condition.
After 6 h of reaction 18% isolated yield of corresponding α-alkylidene
cyclic carbonate was observed (Table 1, entry 1).
Then the same reaction was monitored in presence of our synthesized
cobalt complex 1 as catalyst (0.005 mmol), it was surprised that we got
56% isolated yield of 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one
after 6 h of reaction (Table 1, entry 2). Use of different solvents in the
reaction was checked for the expectation of better yield percentage of
desired product. Instead of increasing the yield percentage of the
product enormous decreased in the product yield was obtained (Table 1,
entries 3–8).
After getting lesser yield from those reactions, we decided to use neat
reaction condition for further optimization of catalysis reaction. Utili­
zation of various base such as NEt3 (triethylamine), DABCO (1,4-dia­
zabicyclo[2.2. 2]octane), DIPEA (N, N-diisopropylethylamine), TBD
(1,5,7- triazabicyclo[4.4. 0]dec‑5-ene), TMEDA (tetramethylethylene­
diamine), t-BuOK (potassium tert‑butoxide), Cs2CO3 (caesium carbon­
ate), K2CO3 (potassium carbonate), PPh3 (triphenylphosphine) in place
of DBU in the reaction, the observed results suggested us to use DBU for
the reaction (Table 1, entries 9–17). Then the reaction temperature was
enhanced stepwise from 60 to 90 ◦ C, increased of product yield was
noticed from 60 to 80 ◦ C (Table 1, entries 18, 19). Due to increase of
temperature produced more number of collisions between the substrate
and the active sites of the catalyst as a result yield percentage of product
increased. Further increase of temperature from 80 to 90 ◦ C caused
slight reduction of desired product yield may be because of formation of
side product at that elevated temperature (Table 1, entry 20). Increment
of catalyst loading for the reaction did not alter the isolated yield per­
centage of the product (Table 1, entry 21). No conversion of the reaction
was found when the reaction was performed without base and catalyst
(Table 1, entry 22). Various metal precursors such as cobalt chloride,
cobalt nitrate, cobalt acetate were incorporated as catalyst in position of
complex 1 for the reaction, the obtained results did not compete with the
result appeared by using our synthesized complex 1 catalyst (Table 1,
entries 23–25). In presence of ligand (HL) the catalytic reaction did not
proceeds at all as no product formation was observed after 6 h of reac­
tion duration (Table 1, entry 26). Therefore ligand itself has no effect on
the catalytic reaction. Again the same catalytic reaction was carried out
in presence of ligand and metal precursor (CoCl2⋅6H2O) in 3:1 mole ratio
but the result obtained was almost similar to that of the result when only
metal precursor used as catalyst (Table 1, entry 27). This due to absence
of suitable solvent (i.e. MeCN/DMF) in catalytic reaction medium, no
formation of complex 1 was took place as a result catalytic activity did
not enhance.
A kinetic graph of the reaction at 80 ◦ C in presence complex 1 as
catalyst clearly depicted that 6 h reaction duration was enough for
maximum yield of desired product (Fig. 4).

Table 1
Control experiments result for the catalytic reactiona.
Entry Catalyst (mmol) Base Solvent Temperature ( ◦ C) Time (h) Isolated Yield (%)

1 – DBU – 60 6 18
2 1 (0.005) DBU – 60 6 56
3 1 (0.005) DBU MeCN 60 6 28
4 1 (0.005) DBU DCM 60 6 21
5 1 (0.005) DBU EtOH 60 6 18
6 1 (0.005) DBU THF 60 6 32
7 1 (0.005) DBU DMF 60 6 30
8 1 (0.005) DBU 1,4-doixane 60 6 35
9 1 (0.005) NEt3 – 60 6 40
10 1 (0.005) DABCO – 60 6 30
11 1 (0.005) DIPEA – 60 6 32
12 1 (0.005) TBD – 60 6 28
13 1 (0.005) TMEDA – 60 6 37
14 1 (0.005) t-BuOK – 60 6 18
15 1 (0.005) Cs2CO3 – 60 6 19
16 1 (0.005) K2CO3 – 60 6 23
17 1 (0.005) PPh3 – 60 6 38
18 1 (0.005) DBU – 70 6 72
19 1 (0.005) DBU – 80 6 95
20 1 (0.005) DBU – 90 6 88
21 1 (0.007) DBU – 80 6 95
22 – – – 80 6 00
23 CoCl2⋅6H2O (0.005) DBU – 80 6 37
24 Co(NO₃)₂⋅6H₂O (0.005) DBU – 80 6 29
25 Co(OAc)2⋅4H2O (0.005) DBU – 80 6 34
26 ligand (HL) (0.005) DBU – 80 6 00
27 HL+ CoCl2⋅6H2Ob DBU – 80 6 40
a
Reaction conditions: 2-methyl-3-butyn-2-ol (8 mmol), CO2 balloon, base (8 mmol), homogeneous condition
b
3:1 mole ratio

4
J.N. Goswami et al. Journal of Molecular Structure 1296 (2024) 136868

Table 2
Substrate scope for the catalytic reactiona.
Entry Substrate Product Time Isolated
(h) Yield (%)

1 6 0

2 6 0

Fig. 4. Kinetic graph for the catalytic reaction [reaction conditions: 2-methyl- 3 6 95
3-butyn-2-ol (8 mmol), DBU (8 mmol), 1 (0.005 mmol), CO2 balloon, 80 ◦ C].

After reaching optimum reaction condition for the catalysis [i.e.

propargyl alcohols (8 mmol), DBU (8 mmol), catalyst [Complex 1]
(0.005 mmol), CO2 balloon, 80 ◦ C] we explored the substrate scope for
the reaction by changing R1 and R2 substituent of alcohol (Table 2). No
product was obtained from non substituted and mono substituted
4 7 91
propargyl alcohol (such as prop‑2-yn-1-ol and but‑3-yn-2-ol) (Table 2,
entries1–2). When both substituent were methyl (R1= R2= -Me) (i.e. 2-
methylbut-3-yn-2-ol), maximum product yield was obtained (95%)
through this catalytic reaction after 6 h (Table 2, entry 3). This phe­
nomenon occurred due to “gem effect” (or Thorpe− Ingold effect) where
two gem dimethyl group favoured cyclization due to their mutual
repulsion [66]. Replacement of one methyl substituent by ethyl
group/isopropyl group of propargyl alcohol influenced the reaction
5 8 87
duration as well as the product yield (Table 2, entries 4, 5). When both
R1= R2= -Et (ethyl) further decreased of desired product yield was
noticed (Table 2, entry 6). Thus increase of the size of substituents (i.e.
bulkiness of the group R1 and R2) greatly influenced the isolated product
yield percentage and reaction time [67]. 1-ethynylcyclohexan-1-ol
produced 78% isolated yield of respective product after 10 h of reac­
tion (Table 2, entry 7). When phenyl group was present in R2 position of
propargyl alcohol obtained moderate yield of corresponding carbonates
product (Table 2, entry 8). But the reactivity is not shown by the internal
propargyl alcohol (2-methyl-4-phenylbut-3-yn-2-ol) (Table 2, entry 9)
6 8 89
[64,67].
The literature survey for the comparison of catalytic production of
4,4-dimethyl-5-methylene-1,3-dioxolan-2-one from 2-methylbut-3-yn-
2-ol with previous reports is given in Table 3. Under both homoge­
neous and heterogeneous catalytic conditions those reported catalyst
produced high yield of 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one
under high CO2 pressure [67–71]. Few reports were published where
1 bar CO2 pressure was used for the desired product synthesis [64,72,
73]. Only one cobalt metal containing catalyst was reported where 87%
7 10 78
GLC (Gas Liquid Chromatography) yield is produced for the respective
product under high carbon dioxide pressure in homogenous catalytic
medium [54]. Our synthesized Co(III) metal containing catalyst gave us
high isolated yield (95%) of 4,4-dimethyl-5-methylene-1,3-dioxola­
n-2-one in homogeneous medium under 1 bar CO2 pressure.

3.4. A probable reaction mechanism for carboxylative cyclization of

propargyl alcohols

The Co(III) center in complex 1 which was capable to activate (continued on next page)
propargyl alcohol via the C-atoms of triple bond that was the main
driving force for the effective catalytic cyclic carbonate synthesis. To
perceive the mechanism of the cyclic carbonate production reaction

5
J.N. Goswami et al. Journal of Molecular Structure 1296 (2024) 136868

Table 2 (continued ) Table 3

Entry Substrate Product Time Isolated
Comparison table for the catalytic production of 4,4-dimethyl-5-methylene-1,3-
(h) Yield (%) dioxolan-2-one from 2-methylbut-3-yn-2-ol with previous reports.

8 12 62 Catalyst Reaction conditions Catalytic Yield Reference

nature (%)a

ZnI2 substrate (1.5 mmol), Homogeneous 95 67

base (NEt3 1.5 mmol),
catalyst (0.3 mmol), 1
MPa CO2, 30 ◦ C, 14h
AgOAc substrate (5 mmol), Homogeneous 87 68
catalyst (1 mol%),
DavePhos (2 mol%),
CO2 (20 bar), CH3CN
9 18 0
(10 mL), RT, 16h
(nBu4N)2Ox substrate (0.03 mmol), Homogeneous 100 69
catalyst (2.5 mol%), (99)b
CO2 (80 bar), 80 ◦ C,
24h
Ag@RB-POP substrate (0.5 mmol), Heterogeneous 87 70
a
catalyst (20 mg, 0.01
Reaction condition: substrate (8 mmol), DBU (8 mmol), catalyst 1 (0.005 mol% based on Ag);
mmol), CO2 (1 atm/balloon), 80 ◦ C. base (DBU 0.5 mmol),
CO2 (1 MPa),
acetobitrile (2 mL),
between propargyl alcohol and CO2 catalyzed by complex 1 and the
30 ◦ C, 12 h
hypothetical results were performed using DFT/LanL2Dz for total cat­ Zn@BBAPA-1 substrate (1.5 mmol), Heterogeneous 98 71
alytic interpretation (the calculation methods are in ESI). From the base (DBU 1.5 mmol),
previous studies [64,67–73] and the experimental evidences, it was catalyst (50 mg), CO2
tallied that propargyl alcohol molecule was activated by the coordina­ (1 MPa), 30 ◦ C, 6h
AgN@COF substrate (3 mmol), Heterogeneous 95 64
tion of the cobalt(III) atom of complex 1 by the carbon atom of triple base (DBU 1 mmol),
bonded propargyl alcohol which was responsible for the start-up of the catalyst (25 mg), CO2
mentioned catalysis. The dissociation of one of the Co–O bond of the (1 atm), RT, 3h
phenolate of hexacoordinated octahedral Co(III) complexes is expected Zn@RIO-1 substrate (5 mmol), Heterogeneous 96 72
base (DBU 5 mmol),
to occur which provides a vacant site for the substrate to coordinate
CO2 (1 atm), catalyst
[74]. All the intermediates and transition states with their relative en­ (15 mg), CO2 (1 atm),
ergies for this catalysis are shown in Fig. 5. The first step of catalysis, the room temperature,
active site of catalyst as complex 1 was initially considered as zero for 10h
the full calculations. Basically, the complex 1 was coordinated via Co AgNPs@TzTa- substrate (5 mmol), Heterogeneous 93 73
POP base (DBU 5 mmol),
(III) ion with C-atoms of triple bond (dCo…Cpropargyl =3.28 Å) from catalyst (15 mg), CO2
propargyl alcohol and was forming the TS-I (− 29.65 kcal mol− 1). In (1 atm), RT, 4h
addition, the reaction was catalytically moved forward, in where the CoCp2 substrate (50 mmol), Homogeneous 87c 54
CO2 reacted with propargyl alcohol in the attendance of catalyst to form base (NEt3 3.6 mmol),
catalyst (1 mmol), CO2
simultaneously, Int-1 and TS –2 with respective energy of − 19.33 kcal
(50 kg/cm3), 80 ◦ C, 5h
mol− 1 and − 36.72 kcal mol− 1. Then, the Int-2 (20.29 kcal mol− 1) was 1 substrate (8 mmol), Homogeneous 95 This work
immediately released from Co(III) center to give regeneration of cata­ base (DBU 8 mmol),
lytic initiation by complex 1 and undergoing an intramolecular proton catalyst (0.005 mmol),
transfer in presence of DBU to form the desired product (− 10.89 kcal CO2 (1 atm/balloon),
80 ◦ C, 6h
mol− 1).
a
. Isolated yield;.
b
The plausible mechanism was constructed (Fig. 6) from the experi­ %Conversion (% selectivity);.
c
mental outcomes and theoretical calculations for the catalytic genera­ GLC yield.
tion of cyclic carbonate by the reaction of CO2 and propargyl alcohol.
The well agreed mechanism was compared with the former reports [64, based catalyst. To best of our knowledge, this is the second report where
67–73]. cobalt metal-based catalyst is used for the synthesis of α-alkylidene cy­
clic carbonates via carboxylative cyclization of propargyl alcohols in
4. Conclusion presence of CO2. Therefore, in near future exploration of this green
synthesis of α-alkylidene cyclic carbonates in presence of Co-Schiff base
The Cobalt (III) complex, [Co(L)3].(DMF) (1) of a Schiff base ligand catalyst encourages the researchers more.
was synthesized and structurally characterized through single crystal
XRD which have octahedral geometry. The complex 1 was very much Declaration of Competing Interest
active in the catalytic fixation of carbon dioxide in propargyl alcohols to
fabricate α-alkylidene cyclic carbonates. The catalytic carboxylative The authors declare that they have no known competing financial
cyclization of propargyl alcohols under 1 bar carbon dioxide pressure interests or personal relationships that could have appeared to influence
produce moderate to high yield (62–95%) of α-alkylidene cyclic car­ the work reported in this paper.
bonates from various substrate of propargyl alcohols at 80 ◦ C temper­
ature. No solvent was used during the catalytic syntheses. Again, DFT Data availability
calculations were performed in order to explain the probable mecha­
nism of the catalysis reaction theoretically. There is no very vast Data will be made available on request.
exploration of this type of catalytic reaction in presence of cobalt metal-

6
J.N. Goswami et al. Journal of Molecular Structure 1296 (2024) 136868

Fig. 5. Possible intermediates and transition states with the relative energies catalyzed carboxylative cyclization of propargyl alcohols with carbon dioxide by
complex 1.

Fig. 6. Plausible mechanism for the carboxylative cyclization of propargyl alcohols catalyzed by complex 1 (mentioned bond lengths are in angstrom).

Acknowledgements
M.D gratefully acknowledges and thanks the I-STEM/catalytic grant/
acad-08/2021–2022 for the research support. AHS is thankful to Dep­
utyship for Research and Innovation, Ministry of Education in Saudi
Arabia for funding the project (IFKSUOR3-318-3).
Data centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44)
1223–336–033; or e-mail: deposit@ccdc.cam.ac.uk.
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.molstruc.2023.136868.
References

Supplementary materials
CCDC 2,237,135 contains the supplementary crystallographic data
for 1. These data can be obtained free of charge via www.ccdc.cam.ac.
uk/conts/retrieving.html, or from the Cambridge Crystallographic
[1] A. Otto, T. Grube, S. Schiebahna, D. Stolten, Closing the loop: captured CO2 as a
feedstock in the chemical industry, Energy Environ. Sci. 8 (2015) 3283–3297.
[2] M. Aresta, Carbon Dioxide As Chemical Feedstock, John Wiley & Sons, Weinheim,
2010. ISBN: 9783527324750.
[3] S. Dabral, T. Schau, The use of carbon dioxide (CO2) as a building block in organic
synthesis from an industrial perspective, Adv. Synth. Catal. 361 (2019) 223–246.

7
J.N. Goswami et al.
[4] B. Grignard, S. Gennen, C. Je´roˆme, A.W. Kleij, C. Detrembleur, Advances in the use
of CO2 as a renewable feedstock for the synthesis of polymers, Chem. Soc. Rev. 48
(2019) 4466–4514.
[5] G. Fiorani, W. Guo, A.W. Kleij, Sustainable conversion of carbon dioxide: the
advent of organocatalysis, Green Chem. 17 (2015) 1375–1389.
[6] Q.W. Song, Z.H. Zhou, L.N. He, Efficient, selective and sustainable catalysis of
carbon dioxide, Green Chem. 19 (2017) 3707–3728.
[7] L. Guo, K.J. Lamb, M. North, Recent developments in organocatalysed
transformations of epoxides and carbon dioxide into cyclic carbonates, Green
Chem. 23 (2021) 77–118.
[8] B. Hu, C. Guild, S.L. Suib, J. CO2 Util. 1 (2013) 18–27.
[9] J. Jia, C. Qian, Y. Dong, Y.F. Li, H. Wang, M. Ghoussoub, K.T. Butler, A. Walsh, G.
A. Ozin, Chem. Soc. Rev. 46 (2017) 4631–4644.
[10] Q.W. Song, Z.H. Zhoua, L.N. He, Green Chem. 19 (2017) 3707–3728.
[11] P. Bhanja, A. Modak, A. Bhaumik, ChemCatChem 11 (2019) 244–257.
[12] P. Bhanja, A. Modak, A. Bhaumik, Chem. Eur. J. 24 (2018) 7278–7297.
[13] N. Haque, S. Biswas, P. Basu, I.H. Biswas, R. Khatun, A. Khan, S.M. Islam, New J.
Chem. 44 (2020) 15446–15458.
[14] M. Dolai, U. Saha, S. Biswas, S. Chatterjee, G.S. Kumar, CrystEngComm. 22 (2020)
8374–8386.
[15] P. Sarkar, I.H. Chowdhury, S. Das, S.M. Islam, Mater. Adv. (2022), https://doi.org/
10.1039/D2MA00600F.
[16] R. Sani, T.K. Dey, M. Sarkar, P. Basu, S.M. Islam, Mater. Adv. 3 (2022) 5575–5597.
[17] S. Biswas, D. Roy, S. Ghosh, S.M. Islam, J. Organomet. Chem. 898 (2019), 120877.
[18] A.K. Ghosh, U. Saha, S. Biswas, Z.A. ALOthman, M.A. Islam, M. Dolai, Ind. Eng.
Chem. Res. 61 (2022) 175–186.
[19] V.B. Saptal, B.M. Bhanage, Bifunctional ionic liquids for the multitask fixation of
carbon dioxide into valuable chemicals, ChemCatChem 8 (2016) 244–250.
[20] Y. Yuan, Y. Xie, C. Zeng, D. Song, S. Chaemchuen, C. Chen, F. Verpoort, Green
Chem. 19 (2017) 2936–2940.
[21] C. Xie, J. Song, H. Wu, Y. Hu, H. Liu, Y. Yang, Z. Zhang, B. Chen, B. Han, Green
Chem. 20 (2018) 4655–4661.
[22] S. Dabral, B. Bayarmagnai, M. Hermsen, J. Schießl, Mormul V, A.S.K. Hashmi,
T. Schaub, Org. Lett. 21 (2019) 1422–1425.
[23] S. Biswas, R. Khatun, M. Sengupta, S.M. Islam, Polystyrene supported Zinc complex
as an efficient catalyst for cyclic carbonate formation via CO2 fixation under
atmospheric pressure and organic carbamates production, Mol.Catal. 452 (2018)
129–137.
[24] S. Arshadi, E. Vessally, A. Hosseinian, S. Soleimani-amiri, L. Edjlali, Three-
component coupling of CO2, propargyl alcohols, and amines: an environmentally
benign access to cyclic and acyclic carbamates, Journal of CO₂ Util. 21 (2017)
108–118.
[25] S. Ghosh, A. Ghosh, S. Biswas, M. Sengupta, D. Roy, S.M. Islam, ChemistrySelect 4
(2019) 3961–3972.
[26] P. Sarkar, A.H. Chowdhury, S. Riyajuddin, S. Biswas, K. Ghosh, S.M. Islam, New J.
Chem. 44 (2020) 744–752.
[27] X.D. Li, Q.W. Song, X.D. Lang, Y. Chang, L.N. He, AgI/TMG-promoted cascade
reaction of propargyl alcohols, carbon dioxide, and 2-aminoethanols to 2-
oxazolidinones, ChemPhysChem 18 (2017) 3182–3188.
[28] R. Khatun, S. Biswas, I.H. Biswas, S. Riyajuddin, N. Haque, K. Ghosh, S.M. Islam, J.
CO2 Util. 40 (2020), 101180.
[29] Z. Zhang, Q. Sun, C. Xia, W. Sun, CO2 as a C1 Source: b(C6F5)3-Catalyzed
Cyclization of o-Phenylene-diamines To Construct Benzimidazoles in the Presence
of Hydrosilane, Org. Lett. 18 (2016) 6316–6319.
[30] I.H. Biswas, S. Biswas, M.S. Islam, S. Riyajuddin, P. Sarkar, K. Ghosh, S.M. Islam,
Catalytic synthesis of benzimidazoles and organic carbamates using a polymer
supported zinc catalyst through CO2 fixation, New J. Chem. 43 (2019)
14643–14652.
[31] P. Basu, T.K. Dey, S. Riyajuddin, S. Biswas, K. Ghosh, S.M. Islam, New J. Chem. 44
(2020) 12680–12691.
[32] W.Z. Zhang, H. Li, Y. Zeng, X. Tao, X. Lua, Palladium-catalyzed cyclization reaction
of o -Haloanilines, CO2 and isocyanides: access to quinazoline-2,4(1H,3H)-diones,
Chin.J. Chem. 36 (2018) 112–118.
[33] S. Biswas, R. Khatun, M. Dolai, I.H. Biswas, N. Haque, M. Sengupta, M.S. Islam, S.
M. Islam, Catalytic formation of N3-substituted quinazoline-2,4(1H,3H)-diones by
Pd(II)EN@GO composite and its mechanistic investigations through DFT
calculations, New J. Chem. 44 (2020) 141–151.
[34] T.K. Dey, P. Basu, S. Riyajuddin, S. Biswas, A. Khan, K. Ghosh, S.M. Islam,
ChemistrySelect 5 (2020) 10355–10366.
[35] P. Sarkar, A.H. Chowdhury, S. Riyajuddin, S. Biswas, K. Ghosh, S.M. Islam, New J.
Chem. 44 (2020) 744–752.
[36] R. Khatun, S. Biswas, S. Islam, I.H. Biswas, S. Riyajuddin, K. Ghosh, S.M. Islam,
ChemCatChem 11 (2019) 1303–1312.
[37] A.A.G. Shaikh, S. Sivaram, Chem. Rev. 96 (1996) 951–976.
Journal of Molecular Structure 1296 (2024) 136868
[38] L. Maisonneuve, O. Lamarzelle, E. Rix, E. Grau, H. Cramail, Chem. Rev. 115 (2015)
12407–12439.
[39] Q.W. Song, L.N. He, Adv. Synth. Catal. 358 (2016) 1251–1258.
[40] K. Ohe, H. Matsuda, T. Ishihara, S. Ogoshi, N. Chatani, S. Murai, J. Org. Chem. 58
(1993) 1173–1177.
[41] K. Ohe, H. Matsuda, T. Morimoto, S. Ogoshi, N. Chatani, S. Murai, J. Am. Chem.
Soc. 116 (1994) 4125–4126.
[42] V. Besse, F. Camara, C. Voirin, R. Auvergne, S. Caillol, B. Boutevin, Polym. Chem. 4
(2013) 4545–4561.
[43] Y. Kayaki, M. Yamamoto, T. Ikariya, J. Org. Chem. 72 (2007) 647–649.
[44] H. Zhang, H.B. Liu, J.M. Yue, Chem. Rev. 114 (2014) 883–898.
[45] Y. Zhao, Y. Wu, G. Yuan, L. Hao, X. Gao, Z. Yang, B. Yu, H. Zhang, Z. Liu, Chem.
Asian. J. 11 (2016) 2735. -2340.
[46] N.D. Ca, B. Gabriele, G. Ruffolo, L. Veltri, T. Zanetta, M. Costa, Adv. Synth. Catal.
353 (2011) 133–146.
[47] Y. Kayaki, M. Yamamoto, T. Ikariya, Angew. Chem. 121 (2009) 4258–4261.
[48] Y.B. Wang, Y.M. Wang, W.Z. Zhang, X.B. Lu, J. Am. Chem. Soc. 135 (2013)
11996–12003.
[49] Y.B. Wang, D.S. Sun, H. Zhou, W.Z. Zhang, X.B. Lu, Green Chem 16 (2014)
2266–2272.
[50] H.S. Kim, J.W. Kim, S.C. Kwon, S.C. Shim, T.J. Kim, J. Organomet. Chem. 545
(1997) 337–344.
[51] Y. Gu, F. Shi, Y. Deng, J. Org. Chem. 69 (2004) 391–394.
[52] H.F. Jiang, A. Wang, H.L. Liu, C.R. Qi, Eur. J. Org. Chem. 2008 (2008) 2309–2312.
[53] L. Ouyang, X. Tang, H. He, C. Qi, W. Xiong, Y. Ren, H. Jiang, Adv. Synth. Catal. 357
(2015) 2556–2565.
[54] Y. Inoue, J. Ishikawa, M. Taniguchi, H. Hashimoto, Bull. Chem. Soc. Jpn. 60 (1987)
1204–1206.
[55] K. Iritani, N. Yanagihara, K. Utimoto, J. Org. Chem. 51 (1986) 5499–5501.
[56] J. Hu, J. Ma, Q. Zhu, Q. Qian, H. Han, Q. Mei, B. Han, Green Chem. 18 (2016)
382–388.
[57] T. Kimura, K. Kamata, N. Mizuno, Angew. Chem. Int. Ed. 51 (2012) 6700–6703.
[58] (a) Y. Sasaki, Tetrahedron Lett. 27 (1986) 1573–1574;
(b) C. Bruneau, P.H. Dixneuf, J. Mol. Catal. 74 (1992) 97–107.
[59] J.M. Liu, X.G. Peng, J.H. Liu, S.Z. Zheng, W. Sun, C.G. Xia, Tetrahedron Lett. 48
(2007) 929–932.
[60] X. Peng, F. Li, C. Xia, Synlett (2006) 1161–1164.
[61] Y. Yuan, Y. Xie, C. Zeng, D. Song, S. Chaemchuen, C. Chen, F. Verpoort, Catal. Sci.
Technol. 7 (2017) 2935–2939.
[62] Z. Zhou, C. He, L. Yang, Y. Wang, T. Liu, C. Duan, ACS Catal 7 (2017) 2248–2256.
[63] S. Dabral, B. Bayarmagnai, M. Hermsen, J. Schießl, V. Mormul, A.S.K. Hashmi,
T. Schaub, Org. Lett. 21 (2019) 1422–1425.
[64] S.S. Islam, S. Biswas, R.A. Molla, N. Yasmin, S.M. Islam, ChemNanoMat 6 (2020)
1386–1397.
[65] A. Dutta, S. Biswas, M. Dolai, B.K. Shaw, A. Mondal, S.K. Saha, M. Ali, RSC Adv. 5
(2015) 23855–23864.
[66] M.E. Jung, G. Piizi, Disubstituent effect: theoretical basis and synthetic
applications, Chem. Rev. 105 (2005) 1735–1766.
[67] J. Hu, J. Ma, Q. Zhu, Q. Qian, H. Han, Q. Mei, B. Han, Zinc(II)-catalyzed reactions
of carbon dioxide and propargylic alcohols to carbonates at room temperature,
Green Chem. 18 (2016) 382–385.
[68] S. Dabral, B. Bayarmagnai, M. Hermsen, J. Schießl, V. Mormul, A.S.K. Hashmi,
T. Schaub, Silver-catalyzed carboxylative cyclization of primary propargyl alcohols
with CO2, Org. Lett. 21 (2019) 1422–1425.
[69] B. Grignard, C.G. Ngassamtounzoua, S. Gennen, B. Gilbert, R. Mereau, C. Jerome,
T. Tassaing, C. Detrembleur, Boosting the catalytic performance of organic salts for
the fast and selective synthesis of α-alkylidene cyclic carbonates from CO2 and
propargylic alcohols, ChemCatChem 10 (2018) 2584–2592.
[70] X. Yu, Z. Yang, F. Zhang, Z. Liu, P. Yang, H. Zhang, B. Yu, Y. Zhao, Z. Liu, A rose
bengal-functionalized porous organic polymer for carboxylative cyclization of
propargyl alcohols with CO2, Chem. Commun. 55 (2019) 12475. -1247.
[71] S.S. Islam, N. Salam, R.Ali Molla, S. Riyajuddin, N. Yasmin, D. Das, K. Ghosh, S.
M. Islam, Zinc (II) incorporated porous organic polymeric material (POPs): a mild
and efficient catalyst for synthesis of dicoumarols and carboxylative cyclization of
propargyl alcohols and CO2 in ambient conditions, Mol. Cat. 477 (2019), 110541.
[72] N. Haque, S. Biswas, S. Ghosh, A.H. Chowdhury, A. Khan, S.M. Islam, ACS Appl.
Nano Mater. 4 (2021) 7663–7674.
[73] A. Roy, N. Haque, R. Chatterjee, S. Biswas, A. Bhaumik, M. Sarkar, S.M. Islam,
AgNPs supported over porous organic polymers for the fixation of CO2 on
propargyl alcohols and amines under solvent-free conditions, New J. Chem. 47
(2023) 6673–6684.
[74] H. Ullah, B. Mousavi, H.A. Younus, Z.A.K. Khattak, S. Chaemchuen, S. Suleman,
F. Verpoort, Chemical fixation of carbon dioxide catalyzed via cobalt (III) ONO
pincer ligated complexes, Commun. Chem. 2 (2019) 42.