雷竞技网页版研究和评论——国际期刊雷竞技苹果下载

国际创新研究期刊》的研究在科学、工程和技术

菜单

ISSN在线(2319 - 8753)打印(2347 - 6710)

所有提交的电磁系统将被重定向到在线手稿提交系统。作者请直接提交文章在线手稿提交系统各自的杂志。

合成和表征的Si (IV)与Salen-Type配体复合物

Gurjaspreet辛格
旁遮普大学化学系、昌迪加尔、印度。
相关文章Pubmed,谷歌学者

访问更多的相关文章国际创新研究期刊》的研究在科学、工程和技术

国际创新研究期刊》的研究在科学、工程和技术

文摘

硅(IV)化合物拥有SiN4O2 (1) SiN2O2C2(2、4)和SiN2O2CCl(3)协调框架在高收益的合成反应的O, N, N, O -供体与不同的硅烷即diethoxydiisocyanatosilane salen-type配体L (C2H5O) 2 si (NCO) 2, dichlorodiphenylsilane (Ph2SiCl2) trichlorophenylsilane (PhSiCl3)和dichloromethylphenylsilane (MePhSiCl2)。化合物1 - 4以元素分析,IR, 1 h NMR和13 c NMR光谱

关键字
席夫碱、硅烷、硅(IV)化合物。

介绍
更高的协调(IV)硅复合物在过去的三十年里得到了很多关注[1,2]。大多数这些化合物从硅前体合成而很少找到更高的协调硅复合物作为起始原料。这些化合物的各种化学变化生成的结构和反应性和一系列创新研究近年来努力。很多文章在硅复合物salen-type配体轴承tridendate O, N, O -和tetradendate O, N, N, O -骨架近年来频繁发表[3-11]。higher-coordinate硅的席夫碱配合物可以在关键点找到与披露有关的多种药理应用程序(12、13)。几个席夫碱与大多数过渡金属离子形成螯合物是已知的一个有用的依据有效的发展,选择性和环境友好的杀虫剂。

实验
合成:合成都干燥氮气气氛下进行使用真空玻璃线。溶剂干燥和净化根据标准程序[14]。水杨醛(鼎晖、印度)已经被在减压蒸馏纯化。三乙胺一直在KOH颗粒,通过简单蒸馏收集。水合肼(CDH) Dichlorodiphenylsilane(奥尔德里奇),Dichloromethylphenylsilane(奥尔德里奇)和Trichlorophenylsilane(奥尔德里奇)使用。配体L和Diethoxydiisocynatosilane已经准备在文献中描述的过程(15、16)。描述:红外光谱得到的热科学费舍尔光谱仪。珀金埃尔默模型获得了环境成分分析仪2400中文元素分析仪。多核的核磁共振(1 h、13 c)光谱被记录在一个力量进步II 400和Jeol (AL 300 MHz)光谱仪使用CDCl3作为内部参考和化学变化相对于四甲基硅烷被报道。熔点是未调整的,以梅尔临时II设备使用密封毛细血管。 Synthesis of silicon(IV) compounds Compound 1: Ligand L (1.18 g, 4.95 mmol) was taken in 30 mL dry benzene and stirred for 10 min at room temperature. Then diethoxydiisocynatosilane (1.00 mL, 4.95 mmol) was added dropwise to the mixture. The color of solution changes from light yellow to dark yellow. The mixture was refluxed azeotropically for 4 h at 80 0C. The compound formed was filtered and dried under vacuum. The compound was hygroscopic and soluble in dimethyl sulfoxide. Yield: 71%; mp: 260-262 oC. Anal. Calcd for C16H10N4O4Si: C, 54.85; H, 2.88; N, 15.99. Found: C, 54.74; H, 2.68; N, 15.84. IR (Nujol, KBr, cm-1): 2248 (ν NCO), 1631 (νas C=N), 1040 (νas Si-O), 560 (νas N→Si). 1H NMR (400 MHz, CDCl3/DMSO-d6, 25°C): 7.58-7.62 (m, 4H, Ar-H), 7.98-8.05 (m, 4H, Ar-H), 9.20 (s, 2H, CH=N). 13C NMR (101 MHz, CDCl3/DMSO-d6, 25°C): 115.8, 117.7, 130.9, 131.6 (Ar-C), 159.2 (NCO), 166.1 (CH=N). General Synthetic Procedure for compounds (2-4) To the stirred solution of ligand L in 70 mL dry THF, slightly excess amount of triethylamine was added. After 20 min of stirring, respective silane was added dropwise at 0 0C to synthesize compounds (2-4). The mixture was stirred for 24 h at room temperature. The desired compound was separated from triethylammonium chloride salt upon solubility basis. The compounds (2-4) were filtered under vacuum and purified by washing with dichloromethane and hexane for the removal of salt.
化合物2:化合物2是通过配体L之间的反应(0.95克,3.96更易),三乙胺(1.10毫升,7.93更易)和dichlorodiphenylsilane(1.0毫升,3.96更易)。复合吸湿。收益率:62%。议员:266 - 268摄氏度。肛交。计算的C26H20N2O2Si: C, 74.26;H, 4.79;6.66 N,。发现:C, 74.18;H, 4.68; N, 6.58. IR (Nujol, KBr, cm-1) 1630 (νas C=N), 1040 (νas Si-O), 560 (νas N→Si). 1H NMR (400 MHz, CDCl3/DMSO-d6, 25°C): 6.74-7.72 (m, 18H, Ar-H), 7.94 (s, 2H, CH=N). 13C NMR (101 MHz, CDCl3/DMSO-d6, 25°C): 114.9-145.8 (Ar-C), 160.7 (CH=N).
化合物3:化合物3的解决方案通过搅拌配体L(1.14克,4.76更易),三乙胺(1.33毫升,9.52更易)和trichlorophenylsilane(1.0毫升,4.76更易)。收益率:70%。议员:258 - 260摄氏度。肛交。计算的C20H15ClN2O2Si: C, 63.40;H, 3.99;7.39 N,。发现:C, 63.28;H, 3.87;7.28 N,。 IR (Nujol, KBr, cm-1) 1639 (νas C=N), 1034 (νas Si-O), 556 (νas N→Si). 1H NMR (400 MHz, CDCl3/DMSO-d6, 25°C): 6.76-7.78 (m, 13H, Ar-H), 8.06 (s, 2H, CH=N). 13C NMR (101 MHz, CDCl3/DMSO-d6, 25°C): 116.3-149.1 (Ar-C), 166.5 (CH=N).
化合物4:得到化合物4搅拌溶液的配体L(1.26克,5.26更易),三乙胺(1.47毫升,10.52更易)和dichloromethylphenylsilane(1.0毫升,5.26更易)。收益率:71%。议员:260 - 262摄氏度。肛交。计算的C21H18N2O2Si: C, 70.36;H, 5.06;7.81 N,。发现:C, 70.16;H, 4.98;7.67 N,。 IR (Nujol, KBr, cm-1) 1639 (νas C=N), 1036 (νas Si-O), 557 (νas N→Si). 1H NMR (400 MHz, CDCl3/DMSO-d6, 25°C): 0.86 (s, 3H, CH3), 6.65-7.45 (m, 13H, Ar-H), 7.80 (s, 2H, CH=N). 13C NMR (101 MHz, CDCl3/DMSO-d6, 25°C): 5.38 (CH3), 114.9-134.0 (Ar-C), 160.7 (CH=N).

结果与讨论
合成:研究了化合物1 - 4黄色固体在良好的收益率salen-type配体L与硅烷的反应方案1中描述。酯交换反应合成了化合物1的diethoxydiisocyanatosilane使用Dean-stark与配体L仪器没有任何基础。配体L是反应dichlorodiphenylsilane (Ph2SiCl2) trichlorophenylsilane (PhSiCl3)和dichloromethylphenylsilane (PhMeSiCl2)在0°C的合成硅(IV)复合物2、3和4分别。三乙胺基需要稍微过量盐的形成为triethylammonium氯溶于tetrahyrdofuran。反应混合物进一步激起了24 h和硅(IV)配合物2 - 4被过滤和干燥溶于dimethylsufoxide。复合物的结构被各种光谱技术认证。
图像
红外光谱法:在这些复合物,特征吸收带N→如果观察到在该地区556 - 560 cm - 1分别为化合物1 - 4。红外光谱吸收带在2248 cm - 1显示化合物1 - NCO集团的存在。Si-O债券的伸展带观察到1034 - 1040 cm - 1为化合物1 - 4。分配给该地区的乐队1630 - 1639 cm - 1显示偶氮甲碱组的存在。多核的核磁共振光谱学:多核的核磁共振谱(1 h和13 c)是按照合成复合物。1 h NMR谱,单线态偶氮甲碱质子(CH = N)观察到在该地区为化合物1 - 4和7.80 - -9.20 ppm这个单线态出现在前场的相比配体L支持协调硅与氮偶氮甲碱组。配合物1 - 4的芳香质子在地区6.65 -8.05 ppm,在前场的多重态信号。最在前场的质子化合物4甲基的观察到0.86 ppm。没有酚醛-哦11.79 ppm的氧和硅原子之间的键的形成。在13 c NMR,观察到更多的屏蔽峰值为5.38 ppm甲基直接连接到硅化合物4。 The peak at 159.2 ppm confirmed the presence of NCO group of compound 1. The peaks in region 160.7-166.5 ppm observed due to azomethine carbon in complexes 1-4 and other aromatic peaks supported the structure of complexes 1-4.

结论
我们合成了Si (IV)包含伦型配体配合物1 - 4。硅烷diethoxydiisocyanatosilane ((C2H5O) 2 Si (NCO) 2), Dichlorodiphenylsilane (Ph2SiCl2) Trichlorophenylsilane (PhSiCl3)和Dichloromethylphenylsilane (MePhSiCl2)用于生产新型中性硅化合物含有更高的协调萨伦型配体l .从实验数据,我们得出结论,硅原子在1 - 4 hypervalent和N→如果债券是配位键。

确认
我们感谢大学拨款委员会(UGC),新德里提供财政支持。

引用
  1. Gostevskii B。,Kalikhman, I., Tessier, C. A., Panzner, M. J., Youngs, W. J., Kost, D., ―Hexacoordinate Complexes of Silacyclobutane: Spontaneous Ring Opening and Rearrangement‖, Organometallics, Vol. 24, pp. 5786-5788, 2005.
  2. 徐,c, Baum, t·H。,―Synthesis and Characterization of Neutral cis-Hexacoordinate Bis(β-diketonate) Silicon(IV) Complexes‖, Inorganic Chemistry, Vol. 43, pp. 1568-1573, 2004.
  3. 穆夏,F。,Bohme, U., Roewer, G., ―Preparation, First X-ray Structure Analysis and Reactivity of Hexacoordinate Silicon Compounds with a Tetradentate Azomethine Ligand‖, Chemical Communication, pp. 1289-1290, 1998.
  4. 辛格,m . S。,Singh, P. K., ―A New Class of Organosilicon(IV) Compounds Based Upon Tetradentate (N2O2) Chelating Ligand‖, Main Group Metal Chemistry, Vol. 23, pp. 183-188, 2000.
  5. Wagler, J。,Doert, T., Roewer, G., ―Synthesis of Amines from Imines in the Coordination Sphere of Silicon—Surprising Photo-Rearrangement of Hexacoordinate Organosilanes‖, Angewandte Chemie, Vol. 43, pp. 2441-2444, 2004.
  6. Wagler, J。,Bohme, U., Roewer, G. ―Activation of Si-Si Bond by Hypercoordination–Cleavage of a Disilane and Formation of a Si-C Bond‖ Organometallics, Vol. 23, pp. 6066-6069, 2004.
  7. Wagler, J。,Bohme, U., Brendler, E., Thomas, U., Goutal, S., Mayr, H., Kempf, B., Remennikov, G., Roewer, G., ―Switching between penta- and hexacoordination with salen-silicon-complexes‖, Inorganic Chimca Acta, Vol. 358, pp. 4270-4286, 2005.
  8. Wagler, J。,Roewer, G., ―Intramolecular Interligand Charge Transfer and a Red Hexacoordinate Si-Complex with Salen-Type Ligand vs. Colorless Tetracoordinate Salen-Si-Complexes with Similar Substituents‖, Inorganic Chimca Acta, Vol. 5, pp. 1717-1724, 2007.
  9. 辛格,G。,Garg, M., Pooja, Manu, Singh, J., Girdhar, S., ―Silicon(IV) Complexes of Schiff Base : Preparation and Characterization‖, International Journal of Scientific Engineering and Technology, Vol. 3, pp. 722-724, 2014.
  10. Wagler, J。,Gerlach, D., Böhme, U., Roewer, G., ―Intramolecular Inter-Ligand Charge Transfer in Hexacoordinate Silicon Complexes‖, Organometallics, Vol. 25, pp. 2929-2933, 2006.
  11. 加西亚,G。阿尔瓦雷斯,E。,Marcos-Fernandez, A., Gutierrez, J., ―Hexacoordinated Oligosilanes from a Hexacoordinated Silicon(IV) Complex Containing an O,N,N,O Salen-type and Thiocyanato-N Ligands‖, Inorganic Chemistry, Vol. 48, pp. 4231-4238, 2009.
  12. 左,J。,Bi, C., Fan, Y., Buac, D., Nardon, C., Daniel, K. G., Dou, Q. P., ―Cellular and computational studies of proteasome inhibition and apoptosis induction in human cancer cells by amino acid Schiff base–copper complexes‖, Journal of Inorganic Biochemistry, Vol. 118, pp. 83- 93, 2013.
  13. 南·D。,Yogeeswari, P., Myneedu, V., Saraswati, V., ―Abacavir prodrugs: Microwave-assisted synthesis and their evaluation of anti-HIV activities‖, Bioorganic Medicinal Chemistry Letters, Vol. 16, pp. 2127-2129, 2006.
  14. 沃格尔,我。,―A Text Book of Practical Organic Chemistry‖, 4th Ed., Longman, London, 1978.
  15. Siddiqi, K。他,F。沙,S。,Zaidi, S., ―Route Leading to a Stable M-H-B unit (M = Si, Ge, Sn) the Bidentate and Tridentate Behaviour of Tetrahydroborate‖, Polyhedron, Vol. 12, pp. 1967-1971, 1993.
  16. 安德森,H。,―Ethylsilicon Isothiocyanates. Use of Acidimetry without Weighing‖, Journal American Chemical Society, Vol. 71, pp. 1801- 1803, 1949.