钴催化α-己烯氢甲酰化反应区域选择性研究

何晓飞; 郭靖; 夏洪强; 赵天生

doi:10.1016/S1872-5813(21)60131-7

钴催化α-己烯氢甲酰化反应区域选择性研究

doi: 10.1016/S1872-5813(21)60131-7

宁夏大学化学化工学院省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏银川 750021

基金项目: 宁夏重点研发计划东西部合作项目（2017BY063）资助

详细信息

通讯作者:
E-mail：zhaots@nxu.edu.cn

中图分类号: O643.3
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出版历程
- 收稿日期: 2021-05-07
- 修回日期: 2021-06-20
- 网络出版日期: 2021-07-19
- 刊出日期: 2022-01-25

Study on regioselectivity in cobalt catalyzed hydroformylation of α-hexene

State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry & Chemical Engineering, Ningxia University, Yinchuan 750021, China

Funds: The project was supported by the East-West Cooperation Project, Key R & D Plan of Ningxia (2017BY063)

摘要

摘要: 采用密度泛函理论方法，研究了膦配体(L)配位催化活性中间体HCo(CO)₂L的电子效应和位阻效应，对α-己烯氢甲酰化反应区域选择的影响。膦配体具有强吸电子能力，可提高HCo(CO)₂L的稳定性；同时PPh₃配体具有大的空间位阻，抑制了α-己烯吸附配位至HCo(CO)₂L、以及C=C双键与Co–H键以支链反应路径加成。形成支链烷基Co中间体过渡态反应能垒(B-TS1)与形成直链烷基Co中间体过渡态(L-TS1)的反应能垒差(ΔΔE)为2.73 kcal/mol，表明前者发生相对困难，有利于按直链路经反应。膦配体的电子效应和位阻效应共同决定α-己烯C=C双键与Co–H键加成反应方式，且有利于直链反应路径加成，产物以直链醛为主。
- 钴 /
- 膦配体 /
- α-己烯 /
- 氢甲酰化 /
- 区域选择性 /
- DFT
Abstract: Regioselective effects of electron and steric hindrance of catalytically active intermediate HCo(CO)₂L coordinated by phosphine ligands on α-hexene hydroformylation were studied based on density functional theory. Phosphine ligands have strong electron-attracting capacity that raises the stability of HCo(CO)₂L. PPh₃ with large steric hindrance suppresses the coordination of α-hexene with HCo(CO)₂L as well as the secondary reaction of the C=C with the Co–H via the branched chain pathway. The energy barrier for the transition state containing linear chain alkyl Co intermediate is lower about 2.73 kcal/mol than that for the transition state with branched chain alkyl Co intermediate, indicating that linear chain pathway is dominant in the addition reaction. Both the electron and steric hindrance effects of phosphine ligands determines the pathway of addition reaction between the C=C of α-hexene and the Co–H. The linear chain addition is preferable that mainly produces linear chain aldehydes.
- cobalt /
- phosphine ligand /
- α-hexene /
- hydroformylation /
- regioselectivity /
- DFT

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FIG. 1239. FIG. 1239.

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图 1 HCo(CO)₄催化烯烃氢甲酰化反应机理

Figure 1 Mechanism for HCo(CO)₄ catalyzed hydroformylation

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图 2 Co₂(CO)₈构型

Figure 2 Configurations of Co₂(CO)₈

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图 3 α-己烯嵌入Co−H键形成烷基活化中间体

Figure 3 Intercalation of α-hexene into Co − H to alkyl intermediates

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图 4 过渡态L-TS1(左)与B-TS1(右)几何构型

Figure 4 Geometry of transition states L-TS1 (left) and B-TS1 (right)

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图 5 不同配体配位活性中间体立体图

Figure 5 Graphic models for active intermediates with different ligands

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图 6 氢甲酰化形成支链醛产物路径示意图

Figure 6 Pathway for branched aldehyde in hydroformylation

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图 7 HCo(CO)₂PPh₃催化α-己烯氢甲酰化反应势能示意图

Figure 7 Potential energy for HCo(CO)₂PPh₃ catalyzed hydroformylation

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表 1 膦配体不同垂直配位构型及相对自由能

Table 1 Coordination configurations of phosphine ligands and free energies

Entry	INT1	INT1a	ΔG*/(kcal·mol⁻¹)
1			0.74
2			0.87
3			0.83
4			0.90
5			0.49
6			0.50
*：ΔG = G(INT1a)−G(INT1)

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表 2 α-己烯配位反应的自由能

Table 2 Free energy of coordination of α-hexene


Entry	L	ΔG_r/(kcal·mol⁻¹)
1	CO	−3.82
2	PH₃	−5.10
3	PF₃	−9.90
4	PMe₃	−3.30
5	PPh₃	−3.26
6	PBu₃	−2.77

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表 3 HCo(CO)₂L构象转化相对焓和自由能

Table 3 Enthalpy and free energy of conformational transformation of HCO(CO)₂L

Entry	Equatorial (e)	Axial (a)	ΔH*/ (kcal·mol⁻¹)	ΔG*/ (kcal·mol⁻¹)
1			0	0
2			1.97	0.41
3			1.70	1.05
4			2.72	1.76
5			1.46	1.14
6			1.78	1.47
*：ΔG = G(a−G(e)，ΔH = H(a)−H(e)

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表 4 直链过渡态L-TS1和支链过渡态B-TS1结构参数

Table 4 Structural parameters of L-TS1 and B-TS1

Parameter	L-TS1(B-TS1)
Parameter	CO	PH₃	PF₃	PMe₃	PBu₃	PPh₃
R(C_α–C_β)	1.405(1.400)	1.401(1.402)	1.403(1.402)	1.407(1.406)	1.402(1.406)	1.399(1.400)
R(Co–C_β)	2.291(2.162)	2.193(2.137)	2.214(2.135)	2.187(2.117)	2.199(2.219)	2.214(2.155)
R(Co–C_α)	2.163(2.187)	2.106(2.154)	2.108(2.182)	2.095(2.159)	2.110(2.243)	2.117(2.164)
R(Co–H)	1.544(1.516)	1.516(1.515)	1.514(1.518)	1.524(1.524)	1.512(1.555)	1.513(1.512)
R(Co–P)	−	2.234(2.554)	2.098(2.088)	2.220(2.222)	2.213(2.223)	2.210(2.243)
R(Co–(CO)_ax)	1.770(1.774)	1.765(1.765)	1.768(1.765)	1.751(1.749)	1.748(1.749)	1.754(1.754)
∠(C_α–Co–C_β)	36.6(37.6)	38.0(38.1)	37.8(37.9)	38.3(38.4)	37.9(36.7)	37.6(37.8)
ν*	662i(633i)	502i(557i)	553i(595i)	620i(657i)	545i(716i)	469i(572i)
Bond Length: Å; Bond angle: ν*; Negative eigenvalue of Hessian matrix: cm⁻¹

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表 5 α-己烯嵌入Co−H键过程自由能

Table 5 Free energy of α-hexene intercalation into Co−H

Entry	L	ΔG/(kcal·mol⁻¹)
Entry	L	L-TS1	B-TS1	ΔΔE*	L-INT2	B-INT2	L-INT3	B-INT3
1	CO	6.54	6.68	0.14	−7.14	−7.19	−	−
2	PH₃	6.08	6.59	0.51	−7.15	−7.07	−7.93	−8.97
3	PF₃	5.71	5.07	−0.64	−12.23	−13.25	−9.92	−11.25
4	PMe₃	8.17	9.37	1.20	−3.21	−10.74	−4.68	−8.04
5	PPh₃	5.75	8.48	2.73	−4.71	−4.62	−10.20	−9.85
6	PBu₃	7.43	9.92	2.49	−4.20	−1.27	−8.43	−2.95
*：ΔΔE = ΔG (B-TS1)−ΔG(L-TS1)

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