Biphasic Hydroformylation of 1-Octene Catalyzed by Ionic Rh(Ⅲ)-complex in the Presence of Tertiary Amine Functionalized Ionic Liquid†

doi:10.7503/cjcu20150221

Abstract

Abstract:

The ionic Rh(Ⅲ)-complexes 1a and 2a exhibited poor catalytic performance for hydroformylation of 1-octene without the presence of any auxiliary additive. The involvement of cheap and low-toxic tertiary amines such as Et₃N or N-methylpiperidine could dramatically boost the catalytic performance of compounds 1a and 2a up to turnover frequency(TOF) of 800 h^-1. When piperidinyl-functionalized ionic liquid of [PEmim]BF₄ was dually used as the additive and the solvent, not only the positive roles of N-methylpiperidine in spurring up the activity of compounds 1a and 2a were embodied, but also the easy recovery and recycling of compounds 1a(or 2a)in [PEmim]BF₄ were fulfilled in biphasic hydroformylation. The TOFs of compounds 1a and 2a in [PEmim]BF₄ were gradually decreased in the course of the recycling uses due to the leaching and deactivation of the catalysts.

Key words: Rh-complex, Functionalized ionic liquid, Hydroformylation, 1-Octene, Tertiary amine

CLC Number:

O643.32

TrendMD:

SHI Dingfu, TAN Chen, WANG Peng, LI Yongqi, CHEN Shengjie, LIU Ye. Biphasic Hydroformylation of 1-Octene Catalyzed by Ionic Rh(Ⅲ)-complex in the Presence of Tertiary Amine Functionalized Ionic Liquid^†[J]. Chem. J. Chinese Universities, 2015, 36(8): 1553.

Figures/Tables 5

Scheme 1 Biphasic hydroformylation of 1-octene catalyzed by complexes 1a or 2a in [PEmim]BF4

Fig.1 Single crystal structures of the phosphine-functionalized ionic liquids 1(A), 2(B) and the ionic Rh(Ⅲ)-complex 1a(C)Selected bond distance/nm: compound 1: P1—C13 0.1829(4), P1—C1 0.1820(4), P1—C7 0.1840(4); compound 2: P1—C7 0.1842(2), P1—C14 0.1820(3), P1—C8 0.1829(3); compound 1a: Rh—P 0.2378(15), 0.2378(15); Rh—Cl 0.2341(14), 0.2341(14), 0.2345(13), 0.2345(13).

Table 1 Crystal data and structure refinement for the functionalized ionic liquid 2

Empirical formula	C₂₄H₂₆N₂P·CF₃SO₃	Z	2
Formula weight	522.5	D_calcd/(g·cm^-3)	1.388
Crystal system	Triclinic	μ(Mo Kα)/mm^-1	0.246
Space group	P-1	T/K	296(2)
a/nm	0.98502(9)	λ/nm	0.071073
b/nm	1.13275(11)	Total reflections	14651
c/nm	1.23674(11)	Unique reflections, R_int	4381(0.0232)
α/(°)	97.419(3)	R₁ [I>2σ(I)]	0.0515
β/(°)	107.282(3)	wR₂(all data)	0.1537
γ/(°)	103.712(3)	F(000)	544
V/nm³	1.2501(2)	Goodness-of-fit on F²	1.028

Table 2 Homogeneous hydroformation of 1-octene catalyzed by the ionic Rh(Ⅲ)-complexes in the presence of auxiliary tertiary aminesa

Entry	Rh-complex	Additive	Conv.^b(%)	Sel.^b(%)		L/B^c	TO $F ald d$ /h^-1
Entry	Rh-complex	Additive	Conv.^b(%)	Ald(n+iso)		L/B^c	iso-Octenes
1	1a		47	77	23	2.1	360
2	1a	Et₃N	93	88	12	2.6	820
3	1a	1-Methylpiperidine	96	88	12	2.8	845
4^e	1a	[PEmim]BF₄	88	94	6	2.7	830
5	2a		44	72	28	2.7	320
6	2a	Et₃N	91	87	13	2.6	790
7	2a	1-Methylpiperidine	93	86	14	2.7	800
8^e	2a	[PEmim]BF₄	93	93	7	2.5	865

Table 2 Homogeneous hydroformation of 1-octene catalyzed by the ionic Rh(Ⅲ)-complexes in the presence of auxiliary tertiary aminesa

Entry	Rh-complex	Additive	Conv.^b(%)	Sel.^b(%)		L/B^c	TO $F ald d$ /h^-1
Entry	Rh-complex	Additive	Conv.^b(%)	Ald(n+iso)		L/B^c	iso-Octenes
1	1a		47	77	23	2.1	360
2	1a	Et₃N	93	88	12	2.6	820
3	1a	1-Methylpiperidine	96	88	12	2.8	845
4^e	1a	[PEmim]BF₄	88	94	6	2.7	830
5	2a		44	72	28	2.7	320
6	2a	Et₃N	91	87	13	2.6	790
7	2a	1-Methylpiperidine	93	86	14	2.7	800
8^e	2a	[PEmim]BF₄	93	93	7	2.5	865

Table 3 Biphasic hydroformylation of 1-octene catalyzed by compounds 1a and 2a in piperidyl-functionalized ionic liquid of [PEmim]BF4 respectivelya

Run	1a-[PEmim]BF₄					2a-[PEmim]BF₄
	Conv.^b(%)	Sel.^b(%)		L/B^c	TOF^d/h^-1	Conv.^b(%)	Sel.^b(%)		L/B^c	TOF^d/h^-1
	Conv.^b(%)	Nonanal		L/B^c	TOF^d/h^-1	iso-Octenes			Nonanal	iso-Octenes
1	90	94	7	1.2	280	98	90	10	2.1	290
2	91	93	7	2.4	280	83	66	34	1.6	180
3	94	93	7	2.0	290	63	65	35	2.2	140
4	89	86	14	1.3	255	58	46	54	1.6	90
5	87	67	33	2.2	195	55	32	68	2.3	60

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