Novel Ir-Complexes for Hydroformylation of Olefins with H2O as the Hydrogen Source

doi:10.6023/cjoc202104025

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (9): 3571-3577.DOI: 10.6023/cjoc202104025 Previous Articles Next Articles

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新型铱配合物催化水作氢源的氢甲酰化反应

刘欢, 林旭锋^*(), 杨妲^*()

中国石油大学(华东)理学院化学系山东青岛 266580

收稿日期:2021-04-12 修回日期:2021-05-25 发布日期:2021-07-12
通讯作者: 林旭锋, 杨妲
基金资助:
国家自然科学基金(21576291); 山东省自然科学基金(ZR2014BM002); 中国博士后科学基金(2019M662460); 青岛市博士后基金(05TB2010001); 自主创新科研计划(20CX06032A)

Novel Ir-Complexes for Hydroformylation of Olefins with H₂O as the Hydrogen Source

Huan Liu, Xufeng Lin(), Da Yang()

Department of Chemistry, College of Science, China University of Petroleum, Qingdao, Shandong 266580

Received:2021-04-12 Revised:2021-05-25 Published:2021-07-12
Contact: Xufeng Lin, Da Yang
Supported by:
National Natural Science Foundation of China(21576291); Natural Science Foundation of Shandong Province(ZR2014BM002); China Postdoctoral Science Foundation(2019M662460); Postdoctoral Applied Research Project of Qingdao City(05TB2010001); Fundamental Research Funds for the Central Universities(20CX06032A)

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Abstract

A series of novel Ir-complexes, namely Ir-L1, Ir-L2, Ir-L3 and Ir-L4, where L1~L4 represent phosphine ligands having different electronic and steric effects, were synthesized in this work. Then the effect of the as-synthesized phosphine ligands on the performance of the Ir(I)-complexes catalysts was investigated for the hydroformylation reaction using H₂O as the hydrogen source. It was found that the Ir-complex modified by the ionic bi-dentate phosphines L4 with a strong π-accepting ability (¹J³¹P-⁷⁷Se =781 Hz) can effectively promote water gas shift reaction (WGSR) and hydroformylation of olefins at the same time. As a result, a 1-hexene conversion of 93% was obtained, and the total yields of the target (linear and branched) aldehydes were up to 93% when using the Ir-L4 catalyst. Meanwhile, the yield of hexane from the hydrogenation of 1-hexene was less than 1%, showing that the side reaction of olefin hydrogenation can be almost completely inhibited when using H₂O as the hydrogen source. Moreover, by using the ionic liquid of [MePh₃P]Br as the solvent, Ir-L4 catalyst can be efficiently recovered for at least 5 times.

Key words: ionic phosphines, iridium complexes, hydroformylation, water gas shift reaction

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Huan Liu, Xufeng Lin, Da Yang. Novel Ir-Complexes for Hydroformylation of Olefins with H₂O as the Hydrogen Source[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3571-3577.

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Fig. & Tab. 8

Scheme 1. A series of novel Ir-complexes catalyzed hydroformylation of olefins with H2O as the hydrogen source

Figure 1. Molecular models of Ir-L2, Ir-L3 and Ir-L4 deduced from the single crystal results (the hydrogen atoms and the solvent molecules are omitted for clarity)

Ir-complex	Selected bond length/nm			Bond angle/(^o)
Ir-complex	Ir—P1	Ir—P2	Ir—C_CO	P1—Ir—P2
Ir-L2	0.23145(19)	0.23173(19)	0.18509(12)	176.65(7)
Ir-L3	0.23177(10)	0.23301(10)	0.18629(56)	173.85(3)
Ir-L4	0.23147(31)	0.23152(30)	0.18309(11)	173.79(11)
Ir(CO)(PPh₃)₂Cl	0.23309(10)	—	0.17911(13)	180.00(-)

Table 1. Selected bond distances and bond angles in the Ir-complexes studied in this work

Figure 2. TG/DTG analyses of the Ir-complexes in air flow

Entry	Cat.	Conv.^b/%	Sel.^b/%			Yield/%	L/B^b
Entry	Cat.	Conv.^b/%	Aldehyde	Isomer	hexane	Yield/%	L/B^b
1	Ir-L1	72	99	<1	<1	72	77/23
2	Ir-L2	87	99	<1	<1	87	78/22
3	Ir-L3	76	99	<1	<1	76	76/24
4	Ir-L4	94	99	<1	<1	94	82/18
5^c	Ir-PPh₃	57	99	<1	<1	87	73/27
6	—	12	99	<1	<1	12	72/28
7^d	Ir-L4	93	75	2	23	70	80/20

Table 2. Different Ir-complexes catalyzed hydroformylation of 1-hexene with H2O as the hydrogen sourcea

Figure 3. Recycling uses of Ir-L4 for hydroformylation of 1- hexene with H2O as hydrogen source (Ir-L4 1.0 mol%, 1-hexene 5.0 mmol, [MePh3P]Br 2.0 g, NMP 2 mL, H2O 0.3 g, CO 4.0 MPa, temperature 140 ℃)

Scheme 2. Proposed catalytic mechanism over Ir-L4 for hydroformylation of olefins with H2O

Major product

Table 3. Generality of Ir-L4 for hydroformylation of olefina

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新型铱配合物催化水作氢源的氢甲酰化反应

Novel Ir-Complexes for Hydroformylation of Olefins with H₂O as the Hydrogen Source

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