桥连双(酮亚胺)和双(二酮亚胺)及其铝配合物的合成与催化活性

doi:10.7503/cjcu20130664

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (3): 524.doi: 10.7503/cjcu20130664

桥连双(酮亚胺)和双(二酮亚胺)及其铝配合物的合成与催化活性

黄庆东^1,², 李春兰², 张宇², 崔立山¹, 朱百春³, 义建军³, 刘林⁴, 郝海军⁴()

1. 中国石油大学(北京)理学院材料科学与工程系, 北京102249
2. 中国石油天然气股份有限公司华北化工销售分公司, 北京100009
3. 中国石油天然气股份有限公司石油化工研究院合成树脂重点实验室, 北京 100195
4. 北京化工大学理学院有机化学系, 北京 100029

收稿日期:2013-07-16 出版日期:2014-03-10 发布日期:2019-08-01
作者简介:联系人简介: 郝海军, 男, 博士, 副教授, 主要从事金属有机化学与催化研究. E-mail: hjhao@mail.buct.edu.cn
基金资助:
中国石油天然气集团公司科技项目(批准号: 09-YK-05-19)资助

Synthesis and Catalytic Activity of Aluminum Complexes Supported by Bis(β-ketimine) and Bis(β-diketimine) Ligands^†

HUANG Qingdong^1,², LI Chunlan², ZHANG Yu², CUI Lishan¹, ZHU Baichun³, YI Jianjun³, LIU Lin⁴, HAO Haijun^4,^*()

1. Department of Materials Science and Engineering, College of Science, China University of Petroleum(Beijing), Beijing 102249, China
2. Petrochina North China Chemicals Marketing Company, Beijing 100009, China
3. Key Laboratory of Synthetic Resin, Petrochemical Research Institute, PetroChina Company Limited, Beijing 100195, China
4. Department of Organic Chemistry, College of Science, Beijing University of Chemical Technology, Beijing 100029, China

Received:2013-07-16 Online:2014-03-10 Published:2019-08-01
Contact: HAO Haijun E-mail:hjhao@mail.buct.edu.cn
Supported by:
† Supported by the Science and Technology Project of Petrochina Company Limited(No.09-YK-05-19).

摘要/Abstract

摘要：

通过桥连双β-二酮类化合物与取代苯胺反应, 合成了5个新的桥连双(β-单酮亚胺)化合物(1~5)和2个新的桥连双(β-二酮亚胺)化合物(6,7), 它们与三甲基铝反应, 得到了相应的3个双(β-酮亚胺基)二铝配合物(8~10)和2个双(β-二酮亚胺基)二铝配合物(11,12). 采用核磁共振、红外光谱和质谱等对这些化合物进行了表征, 通过X射线单晶衍射分析证实了铝配合物的结构, 并考察了这些铝配合物在ε-己内酯开环聚合反应中的催化活性.

关键词: 桥连双(β-酮亚胺), 桥连双(β-二酮亚胺), 铝, 晶体结构, 催化活性

Abstract:

Owing to its special physical and chemical properties as well as good coordination activity with transition metals, β-diketone-derived β-ketimines and β-diketimines have been extensively studied in recent years. In this work, five new bridged bis(β-ketimine)(1—5) and bis(β-diketimine) ligands(6,7) were synthesized by the condensation reaction of 3,3'-(1,4-phenylene)bis(2,4-pentanedione) with various anilines. Treatment of these ligands with AlMe₃ afforded five new aluminum complexes(8—12). All these compounds were characterized via elemental analysis, ¹H NMR, ¹³C NMR, ESI-MS and IR spectroscopy. Structures of two aluminium complexes were determined by the X-ray single-crystal diffraction analysis. The bridged β-ketimine acted as a chelating N, O-bidentate ligand to the aluminium atom. Each aluminum atom showed a distorted tetrahedral coordination geometry. These aluminum complexes exhibited effective catalytic activity in the ring-opening polymerization of ε-caprolactone.

Key words: Bridged bis(β-ketimine), Bridged bis(β-diketimine), Aluminum, Crystal structure, Catalytic activity

中图分类号:

O627

TrendMD:

黄庆东, 李春兰, 张宇, 崔立山, 朱百春, 义建军, 刘林, 郝海军. 桥连双(酮亚胺)和双(二酮亚胺)及其铝配合物的合成与催化活性. 高等学校化学学报, 2014, 35(3): 524.

HUANG Qingdong, LI Chunlan, ZHANG Yu, CUI Lishan, ZHU Baichun, YI Jianjun, LIU Lin, HAO Haijun. Synthesis and Catalytic Activity of Aluminum Complexes Supported by Bis(β-ketimine) and Bis(β-diketimine) Ligands^†. Chem. J. Chinese Universities, 2014, 35(3): 524.

图/表 5

Scheme 1 Synthetic routes of bis(β-ketimine)s and bis(β-diketimine)s as well as their aluminium complexes

Table 1 Crystal data and refinement parameters for complexes 8 and 10

Complex	8	10
Formula	C₃₆H₄₆Al₂N₂O₂	C₃₈H₅₀Al₂N₂O₂
Formula weight	592.71	620.76
Crystal size	0.64 mm×0.58 mm×0.18 mm	0.43 mm×0.30 mm×0.20 mm
Crystal system	Triclinic	Triclinic
Space group	P $1 ˉ$	P $1 ˉ$
a/nm	0.7733(2)	0.8151(2)
b/nm	0.8122(2)	0.8181(3)
c/nm	1.5506(4)	1.5797(4)
α/(°)	77.693(8)	95.53(2)
β/(°)	80.114(8)	97.33(1)
γ/(°)	64.744(6)	116.814(8)
V/nm³	0.8569(3)	0.9182(4)
Z	1	1
D_c/(g·cm^-3)	1.149	1.123
F(000)	318	334
μ/mm^-1	0.117	0.112
θ Range/(°)	2.70—29.99	2.83—29.00
No. of measured reflections	10177	11055
No. of unique reflections(R_int)	4873(0.0261)	4811(0.0325)
No. of observed reflections([I>2σ(I)])	3930	3738
No. of parameters	196	205
GOF	1.0001	1.003
R₁, wR₂ [I>2σ(I)]	0.0449, 0.1143	0.0627, 0.1274

Table 1 Crystal data and refinement parameters for complexes 8 and 10

Complex	8	10
Formula	C₃₆H₄₆Al₂N₂O₂	C₃₈H₅₀Al₂N₂O₂
Formula weight	592.71	620.76
Crystal size	0.64 mm×0.58 mm×0.18 mm	0.43 mm×0.30 mm×0.20 mm
Crystal system	Triclinic	Triclinic
Space group	P $1 ˉ$	P $1 ˉ$
a/nm	0.7733(2)	0.8151(2)
b/nm	0.8122(2)	0.8181(3)
c/nm	1.5506(4)	1.5797(4)
α/(°)	77.693(8)	95.53(2)
β/(°)	80.114(8)	97.33(1)
γ/(°)	64.744(6)	116.814(8)
V/nm³	0.8569(3)	0.9182(4)
Z	1	1
D_c/(g·cm^-3)	1.149	1.123
F(000)	318	334
μ/mm^-1	0.117	0.112
θ Range/(°)	2.70—29.99	2.83—29.00
No. of measured reflections	10177	11055
No. of unique reflections(R_int)	4873(0.0261)	4811(0.0325)
No. of observed reflections([I>2σ(I)])	3930	3738
No. of parameters	196	205
GOF	1.0001	1.003
R₁, wR₂ [I>2σ(I)]	0.0449, 0.1143	0.0627, 0.1274

Fig.1 Molecular structures of complexes 8(A) and 10(B)Symmetry operation: -x, -y, -z.

Table 2 Selected bond lengths(nm) and bond angles(°) for complexes 8 and 10

Complex 8		Complex 10
Al1—O1	0.1796(1)	Al1—O1	0.1797(1)
Al1—N1	0.1940(1)	Al1—N1	0.1944(1)
C9—O1	0.1310(1)	C9—O1	0.1310(2)
C7—N1	0.1319(1)	C7—N1	0.1322(2)
C7—C8	0.1448(2)	C7—C8	0.1447(2)
C8—C9	0.1379(2)	C8—C9	0.1380(2)
C17—Al1—C18	115.42(8)	C18—Al1—C19	115.03(9)
N1—Al1—O1	93.72(4)	N1—Al1—O1	93.29(5)
N1—Al1—C18	112.43(7)	N1—Al1—C18	112.28(7)
Al1—O1—C9	127.46(8)	Al1—O1—C9	126.3(1)
Al1—N1—C7	124.49(9)	Al1—N1—C7	124.09(9)
C6—N1—C7	120.2(1)	C1—N1—C7	119.4(1)
O1—C9—C8	124.3(1)	O1—C9—C8	124.3(1)
C7—C8—C9	123.4(1)	C7—C8—C9	123.0(1)
C8—C7—N1	122.3(1)	C8—C7—N1	122.3(1)

Table 3 Ring-opening of polymerization of ε-caprolactone initiated by complexes 8—10*

Entry	Catalyst	ε-Caprolactone/g	Temp./℃	M_n	PDI	Yield(%)
1	8	7.70	60	26736	1.94	85
2	8	7.70	100	21438	1.76	93
3	9	6.30	60	36771	1.89	89
4	9	6.30	100	23974	1.61	92
5	10	7.30	60	23120	1.91	91
6	10	7.30	100	22976	1.70	95

参考文献 22

[1]	Yu R. C., Hung C. H., Huang J. H., Inorg. Chem., 2002, 41, 6450—6455
[2]	He X., Yao Y., Luo X., Zhang J., Liu Y., Zhang L., Wu Q., Organometallics,2003, 22, 4952—4957
[3]	Zhang L., Brookhart M., White P. S., Organometallics,2006, 25, 1868—1874
[4]	Song P. D., Ye W. P., Wang Y. X., Li Y. S., Organometallics,2009, 28, 5697—5704
[5]	Lyashenko G., Saischek G., Pal A., Herbst-Irmer R., Moesch-Nanetti N.C.,Chem. Commun., 2007, 701—703
[6]	Hao H., Cui C., Roesky H.W., Bai G., Schmidt H. G., Noltemeyer M.,Chem. Commun., 2001, 1118—1119
[7]	Cui C., Roesky H., Schmidt H.G., Noltemeyer M., Hao H., Cimpoesu F., Angew. Chem. Int. Ed., 2000, 39, 4274—4276
[8]	Bourget-Merle L., Lappert M. F., Severn J. R., Chem. Rev., 2002, 102, 3031—3065
[9]	Bai G., Peng Y., Roesky H. W., Li J., Schmidt H. G., Noltemeyer M., Angew. Chem. Int. Ed., 2003, 42, 1132—1135
[10]	Bai G., Wei P., Das A.K., Stephan D. W.,Dalton Trans., 2006, 1141—1146
[11]	Neculai D., Roesky H. W., Neculai A. M., Magull J., Schmidt H. G., Noltemeyer M., J. Organomet. Chem., 2002, 643/644, 47—52
[12]	Dove A.P., Gibson V. C., Marshall E. L., White A. J. P., Williams D. J.,Dalton Trans., 2004, 570—578
[13]	Hao H. J., Han X. M., Synthesis and Application of Carbon-linked Bis(β-ketiminato)aluminum Complexes CN 101302230,2008-11-12
	(郝海军, 韩秀敏. 碳桥联双酮单亚胺基铝配合物的合成及应用, CN 101302230, 2008-11-12)
[14]	Zhang F.L., Synthesis and Structural Characterization of Aluminum, Zinc, and Nickel Complexs Derived from the Novel Linked β-Bis(diketimine) Ligands, Beijing University of Chemical Tecnology, Beijing, 2006
	(张发良. 碳桥联双β-酮二亚胺基铝、锌和镍配合物及碳桥联双β-酮二亚胺二氯化镍配合物的合成和结构表征, 北京: 北京化工大学, 2006)
[15]	Ramirez F., Bhatia S. B., Patwardhan A. V., Smith C. P., J. Org. Chem., 1967, 32, 3547—3553
[16]	Lambert J. B., Liu Z., J. Chem. Crystallogr., 2007, 37, 629—639
[17]	Sheldrick G.M., SHELXS-97, Prgram for X-Ray Crystal Structure Solution, Göttingen University, Göttingen, 1997
[18]	Sheldrick G.M., SHELXL-97, Prgram for X-Ray Crystal Structure Refinement, Göttingen University, Göttingen, 1997
[19]	Neculai D., Neculai A. M., Roesky H. W., Magull J., Bunkòczi G., J. Fluorine Chem., 2002, 118, 131—134
[20]	Gong S., Ma H.,Dalton Trans., 2008, 3345—3357
[21]	Koiwa T., Masuda Y., Shono J., Kawamoto Y., Hoshino Y., Hashimoto T., Natarajan K., Shimizu K., Inorg. Chem., 2004, 43, 6215—5223
[22]	Ma B., Djurovich P. I., Yousufuddin M., Bau R., Thompson M. E., J. Phys. Chem. C,2008, 112, 8022—8031

桥连双(酮亚胺)和双(二酮亚胺)及其铝配合物的合成与催化活性

Synthesis and Catalytic Activity of Aluminum Complexes Supported by Bis(β-ketimine) and Bis(β-diketimine) Ligands^†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 5

参考文献 22

相关文章 15

编辑推荐

Metrics

本文评价

[1]	谭彦, 余申, 吕佳敏, 刘湛, 孙明慧, 陈丽华, 苏宝连. 介孔γ-Al₂O₃微球的高效制备及负载Pd催化剂的性能[J]. 高等学校化学学报, 2022, 43(8): 20220133.
[2]	施耐克, 张娅, SANSON Andrea, 王蕾, 陈骏. Zn(NCN)单轴的负热膨胀性及机理研究[J]. 高等学校化学学报, 2022, 43(6): 20220124.
[3]	陶幸福, 韩成龙, 杨扬, 刘堃. 铝纳米粒子表面引发聚合制备核壳纳米结构[J]. 高等学校化学学报, 2022, 43(10): 20220367.
[4]	李海勃, 肖长发, 江龙, 黄云, 淡宜. MCM-41分子筛负载氯化铝催化丙烯酸甲酯与1-辛烯共聚[J]. 高等学校化学学报, 2021, 42(9): 2974.
[5]	柳扬, 李清波, 孙杰, 赵显. Ga对在AlN衬底上直接生长石墨烯的远程催化[J]. 高等学校化学学报, 2021, 42(7): 2271.
[6]	岳胜利, 武光宝, 李星, 李康, 黄高胜, 唐翌, 周惠琼. 准二维钙钛矿太阳能电池的研究进展[J]. 高等学校化学学报, 2021, 42(6): 1648.
[7]	王宇翔, 余申, 刘湛, 吕佳敏, 李小云, 陈丽华, 苏宝连. 一步液滴法合成酸性和孔道属性可调的硅铝酸盐载体及其Pd基催化剂的性能研究[J]. 高等学校化学学报, 2021, 42(6): 1826.
[8]	闫鹏泉, 王竟荣, 沈亚星, 左志军, 高志华, 黄伟. CuAl₂O₄尖晶石结构对浆态床一氧化碳加氢性能的影响[J]. 高等学校化学学报, 2021, 42(6): 1846.
[9]	胡学一, 韩璐璐, 方云, 夏咏梅. 氧化铝-延展型表面活性剂的吸附胶束及其吸附增溶[J]. 高等学校化学学报, 2021, 42(3): 843.
[10]	王勇, 董彪, 孙娇, 董德录, 孙连坤. 基于分子筛模板的银/硅铝无定形结构复合材料的合成及光谱性质[J]. 高等学校化学学报, 2021, 42(10): 3233.
[11]	王健羽, 张强, 闫文付, 于吉红. 羟基自由基在沸石分子筛合成中的作用[J]. 高等学校化学学报, 2021, 42(1): 11.
[12]	吴勤明, 王叶青, 孟祥举, 肖丰收. 硅铝沸石分子筛晶化过程再思考[J]. 高等学校化学学报, 2021, 42(1): 21.
[13]	王彬宇, 李莉, 李菁, 靳科研, 张少卿, 张佳楠, 闫文付. 用工业固体废料合成沸石分子筛的研究进展[J]. 高等学校化学学报, 2021, 42(1): 40.
[14]	陈良丹,邹伟,吴亮,夏凡杰,胡执一,李昱,苏宝连. 纳米Al₂O₃包覆富锂锰基正极材料Li_1.2Ni_0.13Co_0.13Mn_0.54O₂的性能研究[J]. 高等学校化学学报, 2020, 41(6): 1329.
[15]	田霞,杨福群,袁伟,赵雷,姚雷,甄小丽,韩建荣,刘守信. 含噁二唑大环冠醚的合成、结构及金属离子识别性能[J]. 高等学校化学学报, 2020, 41(3): 490.

桥连双(酮亚胺)和双(二酮亚胺)及其铝配合物的合成与催化活性

Synthesis and Catalytic Activity of Aluminum Complexes Supported by Bis(β-ketimine) and Bis(β-diketimine) Ligands†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 5

参考文献 22

相关文章 15

编辑推荐

Metrics

本文评价

Synthesis and Catalytic Activity of Aluminum Complexes Supported by Bis(β-ketimine) and Bis(β-diketimine) Ligands^†