Synthesis,Characterization of Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene†

doi:10.7503/cjcu20131246

Abstract

Abstract:

A series of bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) complexes with the general formula [2,6-(ArN═CCl)₂C₅H₃N]NiX₂[Ar=2,6-Me₂C₆H₃, X=Br(1a) or Cl(2a); Ar=2,4,6-Me₃C₆H₂, X=Br(1b) or Cl(2b); Ar=4-Cl-2,6-Me₂C₆H₂, X=Br(1c) or Cl(2c)] were synthesized and characterized by FTIR and elemental analysis. The molecular structures of 1a—1c were further characterized by X-ray single crystal diffraction, and the geometry at the metal centre for all the three complexes can be best described as distorted trigonal bipyramidal. At the presence of ethylaluminum sesquichloride(EASC), all the Ni(Ⅱ)-based complexes performed high activities towards butadiene polymerization at 20 ℃, liquid polybutadienes(PB) with molecular weight of 4700—5200 and medium cis-1,4-PB content(74.8%—77.2%) was obtained. Catalytic activities of the catalysts and the microstructures of the resulting polymers were little depen-dent on the ligand environment and highly dependent on polymerization conditions.

Key words: Bis(arylcarboximidoylchloride)pyridine, Ni(Ⅱ) complex, 1, 3-Butadiene polymerization

CLC Number:

O632.14

TrendMD:

LIU Heng, LIU Li, WANG Feng, JIA Xiangyu, BAI Chenxi, ZHANG Chunyu, ZHANG Xuequan. Synthesis,Characterization of Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene^†[J]. Chem. J. Chinese Universities, 2014, 35(6): 1336.

Figures/Tables 11

Scheme 1 Synthetic process of Ni-based catalysts

Fig.1 Crystal structure of complex 1aMethylene dichloride molecules were omitted for clarity.

Fig.2 Crystal structure of complex 1bMethylene dichloride molecules were omitted for clarity.

Fig.3 Crystal structure of complex 1cMethylene dichloride were omitted for clarity.

Table 1 Crystal data and collection parameters of complexes 1a—1c

Complex	1a	1b·CH₂Cl₂	1c·CH₂Cl₂
Fomula	C₂₃H₂₁Br₂Cl₂N₃Ni	C₂₆H₂₇Br₂Cl₄N₃Ni	C₂₄H₂₁Br₂Cl₆N₃Ni
Molecular weight	628.86	741.84	782.67
Crystal system	Monoclinic	Monoclinic	Monoclinic
Space group	P2₁/c	P2₁/n	P2₁/n
a/nm	1.2328(2)	0.84209(9)	0.82406(5)
b/nm	1.8917(3)	2.2750(2)	2.28681(13)
c/nm	1.2291(1)	1.63727(16)	1.62322(9)
α/(°)	90.0	90.0	90.0
β/(°)	117.610(1)	102.488(2)	101.624(1)
γ/(°)	90.0	90.0	90.0
V/nm³	2.5400(6)	3.0624(5)	2.9962(3)
Z	4	4	4
T/K	188	293	188
D_c/(g·cm³)	1.645	1.609	1.735
μ(Mo Kα)/mm^-1	4.14	3.61	3.87
F(000)	1248	1480	1544
θ_range/(°)	2.2—23.4	2.2—23.1	2.2—25.6
Number of reflections collected	14280(R_int=0.069)	17609(R_int=0.032)	19049(R_int=0.035)
Number of independent reflections	4517	5399	5878
Number of data/restraints/parameters	4517/0/284	5399/0/331	5878/0/329
Goodness of fit	1.002	1.040	1.053
R₁[I>2σ(I)]	0.068	0.065	0.058
wR₂	0.185	0.223	0.189

Table 2 Selected bond distances(nm) and bond angles(°) of complexes 1a—1c

Bond	1a	1b·CH₂Cl₂	1c·CH₂Cl₂
Ni1—N1	0.2191(6)	0.2232(5)	0.2216(5)
Ni1—N2	0.1995(6)	0.1982(5)	0.1981(5)
Ni1—N3	0.2182(6)	0.2257(5)	0.2236(5)
Ni1—Br1	0.24233(16)	0.23226(12)	0.23843(10)
Ni1—Br2	0.23487(14)	0.23845(12)	0.23343(10)
N1—C1	0.1252(11)	0.1252(8)	0.1253(8)
N1—C14	0.1445(9)	0.1447(9)	0.1439(8)
N2—C6	0.1319(10)	0.1315(9)	0.1333(8)
N2—C2	0.1332(10)	0.1350(8)	0.1341(7)
N3—C7	0.1274(10)	0.1249(9)	0.1261(8)
N3—C8	0.1458(10)	0.1455(8)	0.1440(8)
N1—Ni1—N2	76.70(2)	77.40(2)	77.58(19)
N1—Ni1—Br1	96.45(19)	99.78(14)	94.37(13)
N1—Ni1—Br2	99.16(17)	94.49(14)	99.38(13)
N2—Ni1—N3	77.10(2)	75.90(2)	76.40(2)
N2—Ni1—Br1	155.00(2)	141.87(16)	144.06(15)
N2—Ni1—Br2	90.60(19)	98.29(16)	97.07(14)
N3—Ni1—Br1	96.74(19)	97.39(15)	94.25(14)
N3—Ni1—Br2	99.05(17)	95.34(15)	98.33(14)
N1—Ni1—N3	150.6(2)	152.6(2)	153.43(19)
Ni1—N1—C14	127.7(5)	128.2(4)	127.7(4)
Ni1—N3—C8	127.1(5)	127.9(4)	127.3(4)
C1—N1—C14	120.9(7)	121.4(6)	127.7(4)
C7—N3—C8	120.8(6)	122.1(6)	127.3(4)

Table 3 Butadiene polymerizatioin results using complexes 1a—1d, 2b—2d as catalystsa

Entry	Cat.	Al agent^b	T/℃	Yield(%)	10^-3 $M n c$	M_w/ $M n c$	Microstructure fraction^d(%)
Entry	Cat.	Al agent^b	T/℃	Yield(%)	10^-3 $M n c$	M_w/ $M n c$	Cis-1,4-PB	1,2-PB	Trans-1,4-PB
1	1a	EASC	20	94.2	5.1	3.2	77.2	0.9	21.9
2	1b	EASC	20	94.0	4.7	3.0	74.8	1.1	24.1
3	1c	EASC	20	92.7	5.0	3.0	75.8	1.1	23.2
4	2a	EASC	20	97.8	5.2	3.1	77.2	1.0	21.8
5	2b	EASC	20	96.0	4.8	3.1	75.4	1.0	23.7
6	2c	EASC	20	96.5	5.2	3.0	76.0	1.2	22.8
7	1b	EASC	-5	23.3	18.6	2.2	89.2	3.3	7.5
8	1b	EASC	50	61.0	4.5	4.0	69.5	1.5	29.0
9	1b	TEA	20	1.8
10	1b	TIBA	20

Table 3 Butadiene polymerizatioin results using complexes 1a—1d, 2b—2d as catalystsa

Entry	Cat.	Al agent^b	T/℃	Yield(%)	10^-3 $M n c$	M_w/ $M n c$	Microstructure fraction^d(%)
Entry	Cat.	Al agent^b	T/℃	Yield(%)	10^-3 $M n c$	M_w/ $M n c$	Cis-1,4-PB	1,2-PB	Trans-1,4-PB
1	1a	EASC	20	94.2	5.1	3.2	77.2	0.9	21.9
2	1b	EASC	20	94.0	4.7	3.0	74.8	1.1	24.1
3	1c	EASC	20	92.7	5.0	3.0	75.8	1.1	23.2
4	2a	EASC	20	97.8	5.2	3.1	77.2	1.0	21.8
5	2b	EASC	20	96.0	4.8	3.1	75.4	1.0	23.7
6	2c	EASC	20	96.5	5.2	3.0	76.0	1.2	22.8
7	1b	EASC	-5	23.3	18.6	2.2	89.2	3.3	7.5
8	1b	EASC	50	61.0	4.5	4.0	69.5	1.5	29.0
9	1b	TEA	20	1.8
10	1b	TIBA	20

Fig.4 Influence of temperature on the microstructures of polybutadienes obtained from 1b/EASC system

Fig.5 FTIR spectrum of polybutadiene obtained in Entry 2, Table 3

Fig.6 1H NMR spectrum of polybutadiene obtained in Entry 2, Table 3

Fig.7 13C NMR spectrum of polybutadiene obtained in Entry 2, Table 3

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