水杨醛亚胺（氨基酚）功能化的氮杂环卡宾稀土溴化物的合成，结构及反应性能
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摘要
通过Ln-N键与咪唑盐B的质解反应,成功地合成并表征了中性的水杨醛亚胺功能化的氮杂环卡宾稀土溴化物L_2SmBr (3-1a),L_2NdBr (3-1b),L_2ErBr (3-1e)以及第一个阳离子型金属钇的溴化物[L_2Y]~+Br- (3-2a);通过该配体的锂盐与三氯化钕的复分解反应,同样得到了配合物L_2NdBr (3-1c);利用正丁基锂对亚胺的加成得到的新型三齿氮杂环卡宾配体,合成了相应的金属锂配合物L’2Li2 (3-3a)和阳离子型氮杂环卡宾镱的溴化物[L’_2Yb]~+Br- (3-3b)。主要结果如下:
1.将LiNiPr2和ErCl3按照4:1的摩尔比反应,首次合成并单晶结构表征了配合物Li(THF)Er(NiPr_2)_4 (3-1d)。
2.将咪唑盐B和Li(THF)Ln(N~iPr_2)_4(Ln = Nd,Sm)按照2∶1的摩尔比在-40°C反应,成功地得到了两例水杨醛亚胺功能化的氮杂环卡宾稀土溴化物(配合物3-1a和3-1b)。将咪唑盐B和正丁基锂按照1∶2的摩尔比反应,然后再与0.5当量的NdCl_3在25°C反应,同样得到了配合物L_2NdBr (3-1c)。产物都经过了元素分析和单晶衍射的表征。
3.将咪唑盐B和Li(THF)Er(NiPr_2)_4按照2∶1的摩尔比在-50°C反应,合成了第一个氮杂环卡宾重稀土卤化物,并得到了第一个氮杂环卡宾铒配合物的晶体结构(配合物3-1e)。
4.将咪唑盐B和Li(THF)Y(NiPr_2)_4按照2∶1的摩尔比在-78°C反应,合成了第一个阳离子型氮杂环卡宾钇配合物(配合物3-2a)。产物经过了元素分析,核磁共振以及单晶衍射的表征。
5.利用正丁基锂在-78°C对亚胺的加成反应,合成了相应的金属锂配合物L’2Li2(配合物3-3a)。产物经过了元素分析,核磁共振以及单晶衍射的表征。
6.将氮杂环卡宾锂配合物L’_2Li_2(配合物3-3a)和YbCl_3按照1∶1的摩尔比在室温反应,合成了阳离子型氮杂环卡宾镱配合物(配合物3-3b)。产物经过了元素分析和单晶衍射的表征。
We synthesized and characterized neutral lanthanide bromides of L_2SmBr (3-1a), L_2NdBr (3-1b), L_2ErBr (3-1e) and the first cation yttrium bromide [L_2Y]~+Br- (3-2a) supported by salicylaldiminato functionalized N-heterocyclic carbene according to the protonolysis of Ln-N bonds by imidazolium salt B. We also synthesized the complexes L_2NdBr (3-1c) by the metathesis reaction of LLi and the NdCl3. We synthesized the complexes L’2Li2 (3-3a) and [L’2Yb]~+Br- (3-3b) via the new trident NHC ligand which synthesized by the addition reaction of n-Buli and imine. The main results as fellows:
1. The amide complex of erbium Li(THF)Er(NiPr_2)_4 (3-1d) was synthesized by the reaction of LiNiPr2 with ErCl3 in the molar ratio of 4:1 and was characterized by X-ray diffraction.
2. Reaction of Li(THF)Ln(NiPr_2)_4 (Ln = Nd, Sm) with imidazolium salt B in the molar ratio of 1:2 at -40°C, gave the complexes L_2NdBr (3-1b) and L_2SmBr (3-1a). Reaction of imidazolium salt B with n-BuLi in the molar ratio of 1:2, then react with 1/2 equiv NdCl_3 at 25°C, also gave the complexes L_2NdBr (3-1c). All complexes were characterized by elemental analysis and X-ray diffraction.
3. Reaction of Li(THF)Er(NiPr_2)_4 with imidazolium salt B in the molar ratio of 1:2 at -50°C, gave the corresponding complexes L_2ErBr (3-1e) which was the first NHC late lanthanide halide and the first crystal structure of an NHC Er halide.
4. Reaction of Li(THF)Y(NiPr_2)_4 with imidazolium salt B in the molar ratio of 1:2 at -78°C, gave the complexes [L_2Y]~+Br- (3-2a) which was the first cation NHC yttrium bromide. It was fully characterized by elemental analysis, ~1H NMR and 13C NMR, X-ray diffraction.
5. By using the addition reaction of n-Buli and imine in at -78°C, we gave the NHC lithium complex L’_2Li_2 (3-3a) which was fully characterized by elemental analysis, 1H NMR and 13C NMR, X-ray diffraction.
6. Reaction of L’_2Li_2 (3-3a) with YbCl3 in the molar ratio of 1:1 at room temperature, gave the corresponding cation NHC ytterbium bromide [L’_2Yb]~+Br- (3-3b). The complexes was characterized by elemental analysis and X-ray diffraction.
1.将LiNiPr2和ErCl3按照4:1的摩尔比反应,首次合成并单晶结构表征了配合物Li(THF)Er(NiPr_2)_4 (3-1d)。
2.将咪唑盐B和Li(THF)Ln(N~iPr_2)_4(Ln = Nd,Sm)按照2∶1的摩尔比在-40°C反应,成功地得到了两例水杨醛亚胺功能化的氮杂环卡宾稀土溴化物(配合物3-1a和3-1b)。将咪唑盐B和正丁基锂按照1∶2的摩尔比反应,然后再与0.5当量的NdCl_3在25°C反应,同样得到了配合物L_2NdBr (3-1c)。产物都经过了元素分析和单晶衍射的表征。
3.将咪唑盐B和Li(THF)Er(NiPr_2)_4按照2∶1的摩尔比在-50°C反应,合成了第一个氮杂环卡宾重稀土卤化物,并得到了第一个氮杂环卡宾铒配合物的晶体结构(配合物3-1e)。
4.将咪唑盐B和Li(THF)Y(NiPr_2)_4按照2∶1的摩尔比在-78°C反应,合成了第一个阳离子型氮杂环卡宾钇配合物(配合物3-2a)。产物经过了元素分析,核磁共振以及单晶衍射的表征。
5.利用正丁基锂在-78°C对亚胺的加成反应,合成了相应的金属锂配合物L’2Li2(配合物3-3a)。产物经过了元素分析,核磁共振以及单晶衍射的表征。
6.将氮杂环卡宾锂配合物L’_2Li_2(配合物3-3a)和YbCl_3按照1∶1的摩尔比在室温反应,合成了阳离子型氮杂环卡宾镱配合物(配合物3-3b)。产物经过了元素分析和单晶衍射的表征。
We synthesized and characterized neutral lanthanide bromides of L_2SmBr (3-1a), L_2NdBr (3-1b), L_2ErBr (3-1e) and the first cation yttrium bromide [L_2Y]~+Br- (3-2a) supported by salicylaldiminato functionalized N-heterocyclic carbene according to the protonolysis of Ln-N bonds by imidazolium salt B. We also synthesized the complexes L_2NdBr (3-1c) by the metathesis reaction of LLi and the NdCl3. We synthesized the complexes L’2Li2 (3-3a) and [L’2Yb]~+Br- (3-3b) via the new trident NHC ligand which synthesized by the addition reaction of n-Buli and imine. The main results as fellows:
1. The amide complex of erbium Li(THF)Er(NiPr_2)_4 (3-1d) was synthesized by the reaction of LiNiPr2 with ErCl3 in the molar ratio of 4:1 and was characterized by X-ray diffraction.
2. Reaction of Li(THF)Ln(NiPr_2)_4 (Ln = Nd, Sm) with imidazolium salt B in the molar ratio of 1:2 at -40°C, gave the complexes L_2NdBr (3-1b) and L_2SmBr (3-1a). Reaction of imidazolium salt B with n-BuLi in the molar ratio of 1:2, then react with 1/2 equiv NdCl_3 at 25°C, also gave the complexes L_2NdBr (3-1c). All complexes were characterized by elemental analysis and X-ray diffraction.
3. Reaction of Li(THF)Er(NiPr_2)_4 with imidazolium salt B in the molar ratio of 1:2 at -50°C, gave the corresponding complexes L_2ErBr (3-1e) which was the first NHC late lanthanide halide and the first crystal structure of an NHC Er halide.
4. Reaction of Li(THF)Y(NiPr_2)_4 with imidazolium salt B in the molar ratio of 1:2 at -78°C, gave the complexes [L_2Y]~+Br- (3-2a) which was the first cation NHC yttrium bromide. It was fully characterized by elemental analysis, ~1H NMR and 13C NMR, X-ray diffraction.
5. By using the addition reaction of n-Buli and imine in at -78°C, we gave the NHC lithium complex L’_2Li_2 (3-3a) which was fully characterized by elemental analysis, 1H NMR and 13C NMR, X-ray diffraction.
6. Reaction of L’_2Li_2 (3-3a) with YbCl3 in the molar ratio of 1:1 at room temperature, gave the corresponding cation NHC ytterbium bromide [L’_2Yb]~+Br- (3-3b). The complexes was characterized by elemental analysis and X-ray diffraction.
引文
[1] Arduengo Ⅲ , A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361
[2] (a)Huang, J.; Schanz, H.; Stevens, E.; Nolan, S.; Organometallics. 1999, 18, 2370 (b)Albert, K.; Gisdekis, P.; Rosch, N. Organometallics. 1998, 17, 1608 (c)Dorta, R.; Stevens, E.; Hoff, C.; Nolan, S. J. Am. Chem. Soc. 2003, 125, 10490
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[8] (a)Nyce, G.; Lamboy, J.; Connor, E.; Waymouth, R.; Hedrick, J. Org. Lett. 2002, 4, 3587 (b)Grasa, G.; Kissling, R. M.; Nolan, S. Org. Lett. 2002, 4, 3583 (c)Grasa, G.; Guveli, T.; Singh, R.; Nolan, S. J. Org. Chem. 2003, 68, 2812 (d) Gardine, M.; Herrmann, W.; Reisinger, C.; Schwarz, J.; Spiegler, M. J. Organomet. Chem 1999, 572, 239
[9] Schumann, H.; Glanz, M.; Winterfeld, J.; Hemling, H.; Kuhn, N.; Kratz, T.; Angew. Chem. Int. Ed. 1994, 33, 1733
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[11] Arnold, P. L.; Mungur, S. A.; Blake, A. J.; Wilson C.; Angew. Chem. Int. Ed. 2003, 42, 5981
[12] (a)Wang, Zhi-Guo; Sun, Hong-Mei; Yao, Hai-Sheng; Yao, Ying-Ming; Shen, Qi; Zhang, Yong J. Organomet. Chem 2006, 691, 3383 (b)Wang, Zhi-Guo; Sun, Hong-Mei; Yao, Hai-Sheng; Shen, Qi; Zhang, Yong Organometallics 2006, 25, 4436
[13] Casely, I. J.; Liddle, S. T.; Blake, A. J.; Wilson, C.; Arnold, P. L. Chem. Commun. 2008, in press
[14] (a)Wang, Bao-Li; Wang Dun, Cui Dong-Mei; Gao, Wei; Tang, Tao; Chen, Xue-Si; Jing, Xia-Bin. Organometallics 2007, 26(13), 3167 (b)Wang, Bao-Li; Cui Dong-Mei; Lv, Kui. Macromolecules 2008, 41, 1983
[15] Edworthy, I. S.; Blake, A. J.; Wilson, C.; Arnold, P. L. Organometallics 2007, 26(15), 3684
[16] (a)Arnold, P. L.; Liddle, S. T. Chem. Commun. 2005, 5638 (b) Liddle, S. T.; Arnold, P. L. Organometallics. 2005, 24, 2597
[17] Arnold, P. L.; Liddle, S. T. Organometallics 2006, 25, 1485
[18] Shukla, P.; Johnson, J. A.; Vidovic, D.; Cowley, A. H.; Abernethy, C. D. J. Chem. Soc., Chem. Commun. 2004, 360
[19] (a) Abernethy, C. D.; Clyburne, J. A. C.; Cowley, A. H.; Jones, R. A. J. Am. Chem. Soc. 1999, 121, 2329 (b) Abernethy, C. D.; Cowley, A. H.; Jones, R. A. J. Organomet. Chem. 2000, 596, 3
[20] Sun, H. M.; Shao, Q.; Hu, D. M.; Li, W. F.; Shen, Q.; Zhang, Y. Organometallics. 2005, 24, 331
[21] Abernethy, C. D.; Macdonald, C. L. B.; Clyburneb, J. A. C.; Cowley, A. H. Chem. Commun. 2001, 61
[22] Arnold, P. L.; Liddle, S. T.; McMaster, J.; Jones, C.; Mills, D. J. Am. Chem. Soc. 2007, 129(17), 5360
[23] Arnold, P. L.; Liddle, S. T. C. R. Chim. 2008, in press
[24] Patel, D.; Liddle, S. T.; Mungur, S. A.; Rodden, M.; Blake, A. J.; Arnold, P. L.Chem. Commun. 2006, 1124
[25] Taylor, M. D.; Carter, C. P. J. Inorg. Nucl. Chem. 1966, 24, 387
[26] Aspinall, C. H.; Tillotson, M. R. Polyhedron. 1994, 13, 3229
[27] Evans, W. J.; Anwander, R.; Ziller, J. W. Inorg. Chem. 1995, 34, 5927
[28] Li, W. F.; Sun, H. M.; Chen, M. Z.; Wang, Z. G.; Hu, D. M.; Shen, Q.; Zhang, Y. Organometallics. 2005, 24, 5925
[29] Arnold, P. L.; Wilson, C. Inorganica Chimica Acta 2007, 360, 190
[30] Deacon, G. B.; Fallon, G. D.; Wilkinson, D. L. J. Organomet. Chem. 1985, 293, 45
[31] (a)Cai, Y. P.; Ma, H. Z.; Kang, B. S.; Su, C. Y.; Zhang, W.; Sun, J.; Xiong, Y. L. J. Organomet. Chem. 2001, 628, 99 (b)Essig, M. W.; Keogh, D. W.; Scott, B. L.; Watkin, J. G. Polyhedron. 2001, 20, 373
[32] 姚海生,苏州大学硕士学位论文,2007
[33] (a)Mungur, S. A.; Liddle, S.T.; Wilson, C.; Sarsfield, M. J.; Arnold, P. L. Chem. Commun. 2004, 2738 (b)Arnold, P. L.; Rodden, M.; Davis, K. M.; Scarisbrick, A. C.; Blake, A. J.; Wilson, C. Chem. Commun. 2004, 1612
[2] (a)Huang, J.; Schanz, H.; Stevens, E.; Nolan, S.; Organometallics. 1999, 18, 2370 (b)Albert, K.; Gisdekis, P.; Rosch, N. Organometallics. 1998, 17, 1608 (c)Dorta, R.; Stevens, E.; Hoff, C.; Nolan, S. J. Am. Chem. Soc. 2003, 125, 10490
[3] (a)Huang, J.; Stevens, E.; Nolan, S.; Petersen, J. J. Am. Chem. Soc. 1999, 121, 2674 (b)Viciu, M.; Kissling, R.; Stevens, E.; Nolan, S. Org. Lett. 2002, 4, 2229 (c)Peris, E.; Loch, J.; Mata, J.; Crabtree, R. Chem. Commun. 2001, 201
[4] (a)Herrmann, W.; Elison, M.; Fischer, J.; Kocher, G.; Artus, G. Angew. Chem. Int. Ed. 1995, 34, 2371 (b) Stauffer, S.; Lee, S.; Stambuli, J.; Hauck, S.; Hartwig, J. Organometallics. 1999, 18, 1596 (c) McGuinness, D.; Cavell, K. Organometallics. 2000, 19, 741 (d)Gstottmayr, C.; Bohm, V.; Herdtweck, E.; Grosche, M.; Herrmann, W. Angew. Chem. Int. Ed. 2002, 41, 1363
[5] Bielawski, C.; Grubbs, R.; Angew. Chem. Int. Ed. 2000, 39, 2903
[6] Perry, M.; Cui, X.; Powell, M.; Hou, D.; Reibenspies, J.; Burgess, K. J. Am. Chem. Soc. 2003, 125, 113
[7] Nyce, G.; Glauser, T.; Connor, E.; Mock, A.; Waymouth, R.; Hedrick, J. J. Am. Chem. Soc. 2003, 125, 3046
[8] (a)Nyce, G.; Lamboy, J.; Connor, E.; Waymouth, R.; Hedrick, J. Org. Lett. 2002, 4, 3587 (b)Grasa, G.; Kissling, R. M.; Nolan, S. Org. Lett. 2002, 4, 3583 (c)Grasa, G.; Guveli, T.; Singh, R.; Nolan, S. J. Org. Chem. 2003, 68, 2812 (d) Gardine, M.; Herrmann, W.; Reisinger, C.; Schwarz, J.; Spiegler, M. J. Organomet. Chem 1999, 572, 239
[9] Schumann, H.; Glanz, M.; Winterfeld, J.; Hemling, H.; Kuhn, N.; Kratz, T.; Angew. Chem. Int. Ed. 1994, 33, 1733
[10] (a) Arduengo, Ⅲ, A. J.; Tamm, M.; McLain, S. J.; Calabrese, J. C.; Davidson, F.; Marshall, W. J.; J. Am. Chem. Soc. 1994, 116, 7927 (b) Herrmann, W. A.; Munck, F.C.; Artus, G.R.J.; Runte, O.; Anwander, R. Organometallics 1997, 16, 682
[11] Arnold, P. L.; Mungur, S. A.; Blake, A. J.; Wilson C.; Angew. Chem. Int. Ed. 2003, 42, 5981
[12] (a)Wang, Zhi-Guo; Sun, Hong-Mei; Yao, Hai-Sheng; Yao, Ying-Ming; Shen, Qi; Zhang, Yong J. Organomet. Chem 2006, 691, 3383 (b)Wang, Zhi-Guo; Sun, Hong-Mei; Yao, Hai-Sheng; Shen, Qi; Zhang, Yong Organometallics 2006, 25, 4436
[13] Casely, I. J.; Liddle, S. T.; Blake, A. J.; Wilson, C.; Arnold, P. L. Chem. Commun. 2008, in press
[14] (a)Wang, Bao-Li; Wang Dun, Cui Dong-Mei; Gao, Wei; Tang, Tao; Chen, Xue-Si; Jing, Xia-Bin. Organometallics 2007, 26(13), 3167 (b)Wang, Bao-Li; Cui Dong-Mei; Lv, Kui. Macromolecules 2008, 41, 1983
[15] Edworthy, I. S.; Blake, A. J.; Wilson, C.; Arnold, P. L. Organometallics 2007, 26(15), 3684
[16] (a)Arnold, P. L.; Liddle, S. T. Chem. Commun. 2005, 5638 (b) Liddle, S. T.; Arnold, P. L. Organometallics. 2005, 24, 2597
[17] Arnold, P. L.; Liddle, S. T. Organometallics 2006, 25, 1485
[18] Shukla, P.; Johnson, J. A.; Vidovic, D.; Cowley, A. H.; Abernethy, C. D. J. Chem. Soc., Chem. Commun. 2004, 360
[19] (a) Abernethy, C. D.; Clyburne, J. A. C.; Cowley, A. H.; Jones, R. A. J. Am. Chem. Soc. 1999, 121, 2329 (b) Abernethy, C. D.; Cowley, A. H.; Jones, R. A. J. Organomet. Chem. 2000, 596, 3
[20] Sun, H. M.; Shao, Q.; Hu, D. M.; Li, W. F.; Shen, Q.; Zhang, Y. Organometallics. 2005, 24, 331
[21] Abernethy, C. D.; Macdonald, C. L. B.; Clyburneb, J. A. C.; Cowley, A. H. Chem. Commun. 2001, 61
[22] Arnold, P. L.; Liddle, S. T.; McMaster, J.; Jones, C.; Mills, D. J. Am. Chem. Soc. 2007, 129(17), 5360
[23] Arnold, P. L.; Liddle, S. T. C. R. Chim. 2008, in press
[24] Patel, D.; Liddle, S. T.; Mungur, S. A.; Rodden, M.; Blake, A. J.; Arnold, P. L.Chem. Commun. 2006, 1124
[25] Taylor, M. D.; Carter, C. P. J. Inorg. Nucl. Chem. 1966, 24, 387
[26] Aspinall, C. H.; Tillotson, M. R. Polyhedron. 1994, 13, 3229
[27] Evans, W. J.; Anwander, R.; Ziller, J. W. Inorg. Chem. 1995, 34, 5927
[28] Li, W. F.; Sun, H. M.; Chen, M. Z.; Wang, Z. G.; Hu, D. M.; Shen, Q.; Zhang, Y. Organometallics. 2005, 24, 5925
[29] Arnold, P. L.; Wilson, C. Inorganica Chimica Acta 2007, 360, 190
[30] Deacon, G. B.; Fallon, G. D.; Wilkinson, D. L. J. Organomet. Chem. 1985, 293, 45
[31] (a)Cai, Y. P.; Ma, H. Z.; Kang, B. S.; Su, C. Y.; Zhang, W.; Sun, J.; Xiong, Y. L. J. Organomet. Chem. 2001, 628, 99 (b)Essig, M. W.; Keogh, D. W.; Scott, B. L.; Watkin, J. G. Polyhedron. 2001, 20, 373
[32] 姚海生,苏州大学硕士学位论文,2007
[33] (a)Mungur, S. A.; Liddle, S.T.; Wilson, C.; Sarsfield, M. J.; Arnold, P. L. Chem. Commun. 2004, 2738 (b)Arnold, P. L.; Rodden, M.; Davis, K. M.; Scarisbrick, A. C.; Blake, A. J.; Wilson, C. Chem. Commun. 2004, 1612
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