Preparation of Cyclic Carbonates from Carbon Dioxide and Epoxides Catalyzed by Bifunctional Molybdenum Complexes

doi:10.6023/cjoc202505003

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (12): 4354-4361.DOI: 10.6023/cjoc202505003 Previous Articles Next Articles

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双功能钼配合物催化二氧化碳和环氧化物制备环状碳酸酯

王涛^a, 陶晟^b^,^*(), 陈飞^a, 杜智宏^a, 薄春博^a, 李敏^a, 刘宁^a^,^*()

^a 石河子大学化学化工学院/化工绿色过程省部共建国家重点实验室培育基地新疆石河子 832003
^b 邵阳学院食品与化学工程学院湖南邵阳 422000

收稿日期:2025-05-04 修回日期:2025-06-20 发布日期:2025-08-18
通讯作者: 陶晟, 陈飞, 刘宁
基金资助:
国家自然科学基金(22478254); 兵团英才、第七师胡杨河市科技计划(QS2024013); 第三师图木舒克市科技计划(KY2025JBGS01)

Preparation of Cyclic Carbonates from Carbon Dioxide and Epoxides Catalyzed by Bifunctional Molybdenum Complexes

Tao Wang^a, Sheng Tao^b^,^*(), Fei Chen^a, Zhihong Du^a, Chunbo Bo^a, Min Li^a, Ning Liu^a^,^*()

^a School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003
^b School of Food and Chemical Engineering, Shaoyang University, Shaoyang, Hunan 422000

Received:2025-05-04 Revised:2025-06-20 Published:2025-08-18
Contact: Sheng Tao, Fei Chen, Ning Liu
Supported by:
National Natural Science Foundation of China(22478254); Bingtuan Talents, the Science and Technology Project of 7th Division Huyanghe City(QS2024013); Science and Technology Project of 3th Division Tumushuke City(KY2025JBGS01)

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Abstract

A single component molybdenum catalyst was synthesized and its activity in the cycloaddition reaction of CO₂ and epoxide was tested. The results show that the molybdenum catalysts exhibit high activity and a broad substrate scope under the reaction conditions of 80 ℃ and 0.5 MPa of CO₂, solvent-free, and and no nucleophilic cocatalysts, affording a wide range of cyclic carbonates in yields of 42%~94%. The reaction mechanism was investigated using in situ infrared (in situ IR), high-resolution mass spectrometry (HRMS) and Fourier transform infrared spectroscopy (FT-IR).

Key words: molybdenum catalyst, epoxide, carbon dioxide, cyclic carbonate

Cite this article

Tao Wang, Sheng Tao, Fei Chen, Zhihong Du, Chunbo Bo, Min Li, Ning Liu. Preparation of Cyclic Carbonates from Carbon Dioxide and Epoxides Catalyzed by Bifunctional Molybdenum Complexes[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4354-4361.

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Fig. & Tab. 8

Scheme 1. Synthesis procedures of the catalyst

Entry	Catalyst	T/℃	p/MPa	Catalyst/ mol%	Isolated yield/%
1	4a	30	1.0	2	14
2	4b	30	1.0	2	11
3	4a	50	1.0	2	56
4	4a	60	1.0	2	78
5	4a	70	1.0	2	89
6	4a	80	1.0	2	94
7	4a	100	1.0	2	93
8	4a	80	0.1	2	54
9	4a	80	0.5	2	94
10	4a	80	1.5	2	92
11	4a	80	0.5	0.5	85
12	4a	80	0.5	1.0	93
13	4a	80	0.5	1.5	93
14	4a	80	0.5	2.5	95

Table 1. Screening of reaction conditionsa

Figure 1. Reaction time on the cycloaddition reaction

Table 2. Substrate scope of epoxidesa

Figure 2. In situ infrared (IR) during the reaction

Figure 3. HRMS spectra of 4ab HRMS m/z

Figure 4. (a) In-situ infrared of cyclic carbonates; (b) Fourier infrared spectrum of the catalyst and the catalyst reacting with the epoxide for 1 h

Scheme 2. Mechanism of the cycloaddition of epoxide with CO2 catalyzed by molybdenum catalysts

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双功能钼配合物催化二氧化碳和环氧化物制备环状碳酸酯

Preparation of Cyclic Carbonates from Carbon Dioxide and Epoxides Catalyzed by Bifunctional Molybdenum Complexes

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Fig. & Tab. 8

References 50

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Entry	Catalyst	T/℃	p/MPa	Catalyst/ mol%	Isolated yield/%
1	4a	30	1.0	2	14
2	4b	30	1.0	2	11
3	4a	50	1.0	2	56
4	4a	60	1.0	2	78
5	4a	70	1.0	2	89
6	4a	80	1.0	2	94
7	4a	100	1.0	2	93
8	4a	80	0.1	2	54
9	4a	80	0.5	2	94
10	4a	80	1.5	2	92
11	4a	80	0.5	0.5	85
12	4a	80	0.5	1.0	93
13	4a	80	0.5	1.5	93
14	4a	80	0.5	2.5	95

Entry	Catalyst	T/℃	p/MPa	Catalyst/ mol%	Isolated yield/%
1	4a	30	1.0	2	14
2	4b	30	1.0	2	11
3	4a	50	1.0	2	56
4	4a	60	1.0	2	78
5	4a	70	1.0	2	89
6	4a	80	1.0	2	94
7	4a	100	1.0	2	93
8	4a	80	0.1	2	54
9	4a	80	0.5	2	94
10	4a	80	1.5	2	92
11	4a	80	0.5	0.5	85
12	4a	80	0.5	1.0	93
13	4a	80	0.5	1.5	93
14	4a	80	0.5	2.5	95

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Entry	Catalyst	T/℃	p/MPa	Catalyst/ mol%	Isolated yield/%
1	4a	30	1.0	2	14
2	4b	30	1.0	2	11
3	4a	50	1.0	2	56
4	4a	60	1.0	2	78
5	4a	70	1.0	2	89
6	4a	80	1.0	2	94
7	4a	100	1.0	2	93
8	4a	80	0.1	2	54
9	4a	80	0.5	2	94
10	4a	80	1.5	2	92
11	4a	80	0.5	0.5	85
12	4a	80	0.5	1.0	93
13	4a	80	0.5	1.5	93
14	4a	80	0.5	2.5	95

Entry	Catalyst	T/℃	p/MPa	Catalyst/ mol%	Isolated yield/%
1	4a	30	1.0	2	14
2	4b	30	1.0	2	11
3	4a	50	1.0	2	56
4	4a	60	1.0	2	78
5	4a	70	1.0	2	89
6	4a	80	1.0	2	94
7	4a	100	1.0	2	93
8	4a	80	0.1	2	54
9	4a	80	0.5	2	94
10	4a	80	1.5	2	92
11	4a	80	0.5	0.5	85
12	4a	80	0.5	1.0	93
13	4a	80	0.5	1.5	93
14	4a	80	0.5	2.5	95

Entry	Catalyst	T/℃	p/MPa	Catalyst/ mol%	Isolated yield/%
1	4a	30	1.0	2	14
2	4b	30	1.0	2	11
3	4a	50	1.0	2	56
4	4a	60	1.0	2	78
5	4a	70	1.0	2	89
6	4a	80	1.0	2	94
7	4a	100	1.0	2	93
8	4a	80	0.1	2	54
9	4a	80	0.5	2	94
10	4a	80	1.5	2	92
11	4a	80	0.5	0.5	85
12	4a	80	0.5	1.0	93
13	4a	80	0.5	1.5	93
14	4a	80	0.5	2.5	95

Entry	Catalyst	T/℃	p/MPa	Catalyst/ mol%	Isolated yield/%
1	4a	30	1.0	2	14
2	4b	30	1.0	2	11
3	4a	50	1.0	2	56
4	4a	60	1.0	2	78
5	4a	70	1.0	2	89
6	4a	80	1.0	2	94
7	4a	100	1.0	2	93
8	4a	80	0.1	2	54
9	4a	80	0.5	2	94
10	4a	80	1.5	2	92
11	4a	80	0.5	0.5	85
12	4a	80	0.5	1.0	93
13	4a	80	0.5	1.5	93
14	4a	80	0.5	2.5	95