Synthesis of Oxygen-bridged Binuclear Titanium and Nickel Complexes and Application in Catalysis of Bimodal Polyethylene†

doi:10.7503/cjcu20180216

Abstract

Abstract:

To explore the potential of oxygen-bridged bisphosphinimine titanium and nickel complexes possessing bimetallic centers as catalysts for olefin polymerization, two oxygen-bridged diphosphorus compounds, named bis-(2-diphenylphosphino) phenylether(1a) and 9,9-dimethyl-4,6-bis(diphenylphosphino)xanthene(1b), were synthesized. After Staudinger reaction with Me₃SiN₃ in toluene under reflux, compound 1a with a flexible diphenyl ether bridge was converted into the bisphosphinimine precusor, while compound 1b with a rigid xanthene bridge was transformed into the monophosphinimine one. Subsequently, the dehalosilylation with CpTiCl₃ afforded the corresponding phosphinimine titanium complexes 3a and 3b, respectively. Single titanium center complex 3b further reacts with NiBr₂(DME) to translate into titaniumnickel heteronuclear bimetallic complex 4b. The structures of the complexes were characterized by ¹H, ¹³C, ³¹P NMR and elemental analyses. And the molecular structures of complexes 3a and 4b were further determined by single-crystal X-ray diffraction analysis. When activated by the methylaluminoxane(MAO), complexes 3a and 4b displayed high catalytic activity for ethylene polymerization. The bimetallic titanium complex 3a produced a wide molecular weight distribution polyethylene product, while the titanium-nickel heteronuclear bimetallic complex 4b gave rise to the bimodal polyethylene product.

Key words: Bridged compound, Phosphinimine, Bimetallic complex, Bimodal polyethylene

CLC Number:

O631
O627

TrendMD:

WANG Tieshi, CHEN Jianjun, YE Lin, ZHANG Aiying, FENG Zengguo. Synthesis of Oxygen-bridged Binuclear Titanium and Nickel Complexes and Application in Catalysis of Bimodal Polyethylene^†[J]. Chem. J. Chinese Universities, 2018, 39(11): 2586.

Figures/Tables 6

References 31

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3a				3b
Ti1—Cl1	0.23011(17)	Cl2—Ti1—Cl1	101.79(5)	Ti1—Cl1	0.23161(19)	Cl1—Ti1—Cl2	104.25(7)
Ti1—N1	0.1766(3)	C24—O1—C23	115.9(3)	Ti1—N1	0.1769(4)	N1—P2—C26	108.0(2)
Ti2—N2	0.1764(3)	N1—Ti1—Cl1	102.67(12)	P1—C1	0.1834(6)	N1—Ti1—Cl1	102.23(16)
P1—N1	0.1593(3)	N2—Ti2—Cl3	103.38(12)	P2—N1	0.1602(4)	C25—C26—P2	115.2(4)
P1—C6	0.1799(4)	C18—P1—N1	109.44(18)	P2—C26	0.1808(5)	C27—O1—C18	118.8(4)
P2—N2	0.1579(3)	C29—P2—N2	112.29(18)	O1—C18	0.1389(6)	C27—C26—P2	125.3(4)
O1—C23	0.1398(5)	P1—N1—Ti1	163.2(2)	O1—C27	0.1380(6)	P2—N1—Ti1	164.7(3)
O1—C24	0.1392(5)	P2—N2—Ti2	158.0(2)

3a				3b
Ti1—Cl1	0.23011(17)	Cl2—Ti1—Cl1	101.79(5)	Ti1—Cl1	0.23161(19)	Cl1—Ti1—Cl2	104.25(7)
Ti1—N1	0.1766(3)	C24—O1—C23	115.9(3)	Ti1—N1	0.1769(4)	N1—P2—C26	108.0(2)
Ti2—N2	0.1764(3)	N1—Ti1—Cl1	102.67(12)	P1—C1	0.1834(6)	N1—Ti1—Cl1	102.23(16)
P1—N1	0.1593(3)	N2—Ti2—Cl3	103.38(12)	P2—N1	0.1602(4)	C25—C26—P2	115.2(4)
P1—C6	0.1799(4)	C18—P1—N1	109.44(18)	P2—C26	0.1808(5)	C27—O1—C18	118.8(4)
P2—N2	0.1579(3)	C29—P2—N2	112.29(18)	O1—C18	0.1389(6)	C27—C26—P2	125.3(4)
O1—C23	0.1398(5)	P1—N1—Ti1	163.2(2)	O1—C27	0.1380(6)	P2—N1—Ti1	164.7(3)
O1—C24	0.1392(5)	P2—N2—Ti2	158.0(2)

Entry	Cat.	Molar ratio of Al/Cat. ^a	Time/min	Temperature/℃	Pressure/MPa	Yield/g	Activity^b	10^-5M_w(GPC)	PDI
1	3a	1600	15	40	0.5	3.25	13.00	5.82	8.3
2	4b	1600	15	40	0.5	1.93	7.72	8.16	22.6
3	4b	400	15	40	0.5	0.64	2.56	3.88	11.4
4	4b	800	15	40	0.5	1.27	5.08	6.73	18.4
5	4b	3200	15	40	0.5	1.78	7.12	6.15	18.6
6	4b	1600	5	40	0.5	0.89	10.68	6.31	12.1
7	4b	1600	10	40	0.5	1.45	8.70	7.55	17.1
8	4b	1600	30	40	0.5	2.31	4.62	8.32	24.5
9	4b	1600	15	20	0.5	1.33	5.32	8.34	23.3
10	4b	1600	15	60	0.5	2.17	8.68	7.38	21.2
11	4b	1600	15	80	0.5	1.84	7.36	4.94	22.2
12	4b	1600	15	40	0.3	1.21	4.84	5.01	19.9
13	4b	1600	15	40	0.7	2.76	11.04	9.93	25.3

Entry	Cat.	Molar ratio of Al/Cat. ^a	Time/min	Temperature/℃	Pressure/MPa	Yield/g	Activity^b	10^-5M_w(GPC)	PDI
1	3a	1600	15	40	0.5	3.25	13.00	5.82	8.3
2	4b	1600	15	40	0.5	1.93	7.72	8.16	22.6
3	4b	400	15	40	0.5	0.64	2.56	3.88	11.4
4	4b	800	15	40	0.5	1.27	5.08	6.73	18.4
5	4b	3200	15	40	0.5	1.78	7.12	6.15	18.6
6	4b	1600	5	40	0.5	0.89	10.68	6.31	12.1
7	4b	1600	10	40	0.5	1.45	8.70	7.55	17.1
8	4b	1600	30	40	0.5	2.31	4.62	8.32	24.5
9	4b	1600	15	20	0.5	1.33	5.32	8.34	23.3
10	4b	1600	15	60	0.5	2.17	8.68	7.38	21.2
11	4b	1600	15	80	0.5	1.84	7.36	4.94	22.2
12	4b	1600	15	40	0.3	1.21	4.84	5.01	19.9
13	4b	1600	15	40	0.7	2.76	11.04	9.93	25.3