芳氧基功能化的氮杂环卡宾稀土配合物的合成，结构和反应性能的研究
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摘要
以芳氧基功能化的氮杂环卡宾前体为辅助配体，合成并表征了芳氧基功能化的氮杂环卡宾稀土胺化物，卡宾断裂的芳氧稀土配合物以及离子对结构的咪唑盐稀土钕配合物，主要结果如下：
1将LiN~iPr_2和SmCl_3按照4：1的摩尔比在THF／己烷混合液中反应，首次合成并单晶结构鉴定了配合物Li(THF)Sm(N~iPr_2)_4(1)。
2将芳氧基功能化的氮杂环卡宾前体[HO-4，6-di_~tBu-C_6H_2-2-CH_2{CH(NCHCH N) ~iPr}] Cl(A)、Li(THF)Ln(N~iPr_2)_4(Ln=Y，Nd，Sm)和n-BuLi按照摩尔比2∶1∶1，在-78℃反应，成功地得到了三例芳氧基功能化的氮杂环卡宾稀土胺化物：[O-4，6-di-~tBu-C_6H_2-2-CH_2-{C(NCHCHN~iPr)}]_2LnN~iPr_2(Ln=Y(2)，Nd(3)，Sm(4))，产物都经过了元素分析，红外，及单晶结构等分析表征，配合物2也经过了~1HNMR，~(13)CNMR的表征。
3初步研究了配合物2，3，4对己内酯，丙交酯的催化聚合活性，发现他们都可以催化己内酯，丙交酯的聚合，聚合物的分子量分布较宽；并尝试了配合物4和小分子PhNCO的插入反应。
4将NaOAr、SmCl_3和[HO-4，6-di-~tBu-C_6H_2-2-CH_2{CH(NCHCHN)Me}]Cl(B)以4∶1∶1摩尔比，采用一锅煮的方法，希望得到芳氧基功能化的氮杂环卡宾稀土芳氧配合物没有取得成功，而是得到了断裂的产物[O-4，6-di-~tBu-C_6H_2-2-[CH{N(CHCH)NMe}]][(O-4，6-di-~tBu-C_6H_2)_2CH_2][O-2，4-di-~tBu-C_6H_3][N(CH(MeN)CHCH)]Sm(THF)(5)。配合物5经过了元素分析，红外及X—单晶结构的分析表征。
5将A、NdCl_3按照2∶1的摩尔比，常温下，在THF中搅拌，反应，经处理，得到了离子对结构的配合物[NdCl_5(THF)]~(2-) [HO-4，6-di-~tBu-C_6H_2 2-CH_2{CH(~iPrNCHCHN)}]_2~+ (6)，6经红外，元素分析，X—单晶结构表征。尝试了配合物6和碱(NaN(SiMe_3)_2，LiN~iPr_2)的反应，希望能用此方法得到氮杂环卡宾稀土卤化物或其衍生物。
We synthesized and characterized lanthanides amide complexes of (Y, Nd, Sm) supported by aryloxo-functional N-heterocyclic carbene, an bridged bisphenoxide complexe of lanthanide from the cleavage of aryloxo-functional N-heterocyclic carbenes and an ion-pairs complex supported by aryloxo-functional N-heterocyclic carbene precursor. The main results as fellows:
1. The amide complex of samarium Li(THF)Sm(N~iPr_2)_4 (1) was synthesized and characterized by the reaction of LiN~iPr_2 with SmCl_3 in 4:1 molar ratio in THF and hexane,
2 Reaction of aryloxo-functional N-heterocyclic carbene precursor [HO-4, 6-di-~tBu-C_6H_2-2-CH_2{CH(NCHCHN)~iPr}]Cl (A) , Li(THF)Ln(N~iPr_2)_4 (Ln= Y, Nd, Sm) and n-BuLi in 2:1:1 molar ratio in THF at -78℃for 10h, and at room temperature for 12h, gave the corresponding complexes [0-4, 6-di-~tBu-C_6H_2-2-CH_2-{C(NCHCHN~iPr)}]_2 LnN~iPr_2 (Ln=Y(2), Nd(3), Sm(4)). All complexes were fully characterized by IR, elemental analysis, X-ray diffraction, and by ~1HNMR and ~(13)CNMR in the case of Y.
3. The catalytic activity of complexes 2, 3 and 4 for e-Caprolactone and L-lactide polymerization were examined. All the complexes can catalyse polymerization of e-Caprolactone and L-lactide, gave the polymers with rather broader molecular weight distribution.
4. Reaction of NaOAr, SmCl_3 and aryloxo-functional N-heterocyclic carbene precursor [HO-4, 6-di-~tBu-C_6H_2-2-CH_2{CH(NCHCHN)Me}]Cl (B) in 4:1:1 molar ratio in THF in one-pot hadn't afforded an anionic phenoxide complex of samarium (5) supported by a bridged bisphenoxo through the cleavage of aryloxo-functional N-heterocyclic carbenes. The complexes 5 was characterized by IR, elemental analysis, X-ray diffraction.
5 Reaction of aryloxo-functional N-heterocyclic carbene precursor A with NdCl_3 in 2:1 molar ratio in THF yielded an ion-pairs complex 6, The complex 6 was characterized by IR, elemental analysis, and X-ray diffraction. The further reaction of 6 with alkali (NaN(SiMe_3)_2, LiN~ipr_2) were tried and no definite complexes were isolated.
1将LiN~iPr_2和SmCl_3按照4：1的摩尔比在THF／己烷混合液中反应，首次合成并单晶结构鉴定了配合物Li(THF)Sm(N~iPr_2)_4(1)。
2将芳氧基功能化的氮杂环卡宾前体[HO-4，6-di_~tBu-C_6H_2-2-CH_2{CH(NCHCH N) ~iPr}] Cl(A)、Li(THF)Ln(N~iPr_2)_4(Ln=Y，Nd，Sm)和n-BuLi按照摩尔比2∶1∶1，在-78℃反应，成功地得到了三例芳氧基功能化的氮杂环卡宾稀土胺化物：[O-4，6-di-~tBu-C_6H_2-2-CH_2-{C(NCHCHN~iPr)}]_2LnN~iPr_2(Ln=Y(2)，Nd(3)，Sm(4))，产物都经过了元素分析，红外，及单晶结构等分析表征，配合物2也经过了~1HNMR，~(13)CNMR的表征。
3初步研究了配合物2，3，4对己内酯，丙交酯的催化聚合活性，发现他们都可以催化己内酯，丙交酯的聚合，聚合物的分子量分布较宽；并尝试了配合物4和小分子PhNCO的插入反应。
4将NaOAr、SmCl_3和[HO-4，6-di-~tBu-C_6H_2-2-CH_2{CH(NCHCHN)Me}]Cl(B)以4∶1∶1摩尔比，采用一锅煮的方法，希望得到芳氧基功能化的氮杂环卡宾稀土芳氧配合物没有取得成功，而是得到了断裂的产物[O-4，6-di-~tBu-C_6H_2-2-[CH{N(CHCH)NMe}]][(O-4，6-di-~tBu-C_6H_2)_2CH_2][O-2，4-di-~tBu-C_6H_3][N(CH(MeN)CHCH)]Sm(THF)(5)。配合物5经过了元素分析，红外及X—单晶结构的分析表征。
5将A、NdCl_3按照2∶1的摩尔比，常温下，在THF中搅拌，反应，经处理，得到了离子对结构的配合物[NdCl_5(THF)]~(2-) [HO-4，6-di-~tBu-C_6H_2 2-CH_2{CH(~iPrNCHCHN)}]_2~+ (6)，6经红外，元素分析，X—单晶结构表征。尝试了配合物6和碱(NaN(SiMe_3)_2，LiN~iPr_2)的反应，希望能用此方法得到氮杂环卡宾稀土卤化物或其衍生物。
We synthesized and characterized lanthanides amide complexes of (Y, Nd, Sm) supported by aryloxo-functional N-heterocyclic carbene, an bridged bisphenoxide complexe of lanthanide from the cleavage of aryloxo-functional N-heterocyclic carbenes and an ion-pairs complex supported by aryloxo-functional N-heterocyclic carbene precursor. The main results as fellows:
1. The amide complex of samarium Li(THF)Sm(N~iPr_2)_4 (1) was synthesized and characterized by the reaction of LiN~iPr_2 with SmCl_3 in 4:1 molar ratio in THF and hexane,
2 Reaction of aryloxo-functional N-heterocyclic carbene precursor [HO-4, 6-di-~tBu-C_6H_2-2-CH_2{CH(NCHCHN)~iPr}]Cl (A) , Li(THF)Ln(N~iPr_2)_4 (Ln= Y, Nd, Sm) and n-BuLi in 2:1:1 molar ratio in THF at -78℃for 10h, and at room temperature for 12h, gave the corresponding complexes [0-4, 6-di-~tBu-C_6H_2-2-CH_2-{C(NCHCHN~iPr)}]_2 LnN~iPr_2 (Ln=Y(2), Nd(3), Sm(4)). All complexes were fully characterized by IR, elemental analysis, X-ray diffraction, and by ~1HNMR and ~(13)CNMR in the case of Y.
3. The catalytic activity of complexes 2, 3 and 4 for e-Caprolactone and L-lactide polymerization were examined. All the complexes can catalyse polymerization of e-Caprolactone and L-lactide, gave the polymers with rather broader molecular weight distribution.
4. Reaction of NaOAr, SmCl_3 and aryloxo-functional N-heterocyclic carbene precursor [HO-4, 6-di-~tBu-C_6H_2-2-CH_2{CH(NCHCHN)Me}]Cl (B) in 4:1:1 molar ratio in THF in one-pot hadn't afforded an anionic phenoxide complex of samarium (5) supported by a bridged bisphenoxo through the cleavage of aryloxo-functional N-heterocyclic carbenes. The complexes 5 was characterized by IR, elemental analysis, X-ray diffraction.
5 Reaction of aryloxo-functional N-heterocyclic carbene precursor A with NdCl_3 in 2:1 molar ratio in THF yielded an ion-pairs complex 6, The complex 6 was characterized by IR, elemental analysis, and X-ray diffraction. The further reaction of 6 with alkali (NaN(SiMe_3)_2, LiN~ipr_2) were tried and no definite complexes were isolated.
引文
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[14] Aspinall, C. H.; Tillotson, M. R. Polyhedron 1994, 73,3229
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[16] Cepanec, I.; Mikuldas, H.; Vinkovic, V. Synth. Commun. 2001,37,2913
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[18] Berich, H. P.; Roesky, W. Angew. Chem. Int. Chem., 1998,37, 1569
[19] Burgstein, M. R.; Berberich; Roesky, P. W. Chem. Eur. J., 2001, 7,14
[20] Evans, W. J.; Katsumata H. Macromolecules, 1994,27, 2330
[21] Hidenori Aihara, Tsukasa Matsuo, Hiroyuki Kawaguchi Chem. Commun. 2003, 2204
[22] Elena Mas-Marzá, Macarena Poyatos, Mercedes Sanaǘ, Eduardo Peris Organometallics, 2004, 23, 323
[23] Caddick, S.; Cloke, F.G. N.; Hitchcock, P. B.; Lewis, A. K. de K. Angew. Chem. Int. Ed. 2004, 43, 5824
[24] Rabe, G. W.; Mei, Z. P.; Riederer, F.A.; Yap, G. P. A. Inorg. Chem. 2003, 42, 3527
[25] Denise Baudry-Barbier, Nicolas Andre, Alain Dormond, Christine Pardes, Philippe Richard, Marc Visseaux, Cheng Jian Zhu Eur. J. Inorg. Chem. 1998, 1721
[26] Mario Glanz, Sebastian Dechert, Herbert Schumann, Dietmar Wolff, Jiirgen Springer Z. Anorg. Allg. Chem. 2000, 626, 2467
[27] Zhang, Li-Lu; Yao, Ying-Ming; Luo,Yun-Jie; Shen,Qi; Sun, Jie Polyhedron 2000, 19, 2243
[28] Xie, Zuowei; Chui, Kwoli; Yang, Qing-chuan; Thomas C. W. Mak, Jie Sun Organometallics 1998, 17, 3937
[29] Ling, Jun; Zhu, Wei-pu; Shen, Zhi-quan Macromolecules 2004, 37, 758
[30] 毛礼胜，浙江大学博士学位论文，1997
[31] 王志国，苏州大学博士学位论文，2006
[32] Csihony, S.; Culkin, D. A.; Sentman, A.; Dove, C. A. P.; Waymouth, R. M.; Hedrick, J. L. J. Am. Chem. Soc. 2005, 127,9079
[33] Connor, E. F.; Nyce, G. W.; Myers, M.; Mock,A.; Hedrick, J. L. J. Am. Chem. Soc. 2002, 124, 914
[34] Arnold, P. L.; Scarisbrick, A. C. Organometallics 2004, 23, 2519
[35] Arnold, P. L.; Blake, A. J.; Wilson, C. Chem. Eur. J. 2005, 11, 6095
[36] Liddle, S. T.; Arnold, P. L. Organometallics 2005, 24, 2597
[37] Cheng, L.; Yang, Y. H.; Luo, M. R.; Zhang, D. R. Inorg. Chim. Acta 1987, 130, 125
[38] Babai, A.; Mudring, A. V. Inorg. Chem. 2005, 44, 8168
[2] Arnold, P. L.; Mungur, S. A.; Blake, A. J.; Wilson C; Angew. Chem. Int. Ed. 2003, 42, 5981
[3] Schumann, H.; Glanz, M.; Winterfeld, J.; Hemling, H.; Kuhn, N.; Kratz, T.; Angew. Chem. Int. Ed. 1994,33,1733
[4] Arduengo, III, A. J.; Tamm, M.; McLain, S. J.; Calabrese, J. C; Davidson, F.; Marshall, W. J.; J. Am. Chem. Soc. 1994,116,7927
[5] Herrmann, W. A.; Munck, F. C; Artus, G. R. J.; Runte, O.; Anwander, R.; Organometallics 1997,16,682
[6] Abernethy, C. D.; Macdonald, C. L. B.; Clyburne, J. A. C; Cowley, A. H.; Chem. Commun., 2001,61
[7] Wang, Zhi-Guo; Sun, Hong-Mei; Yao, Hai-Sheng; Yao, Ying-Ming; Shen, Qi; Zhang, Yong J. Organomet. Chem 2006,691, 3383
[8] Arnold, P. L.; Liaale, S. T. Chem. Commun. 2005,5638
[9] Arnold, P. L.; Rodden, M.; Wilson, C. Chem.Commun. 2005,1743
[10] Arnold, P. L.; Liddle, S. T. Organometallics 2006, 25,1485
[11] Wang, Zhi-Guo; Sun, Hong-Mei; Yao, Hai-Sheng; Shen, Qi; Zhang, Yong Organometallics 2006, 25,4436
[12] Patel, D.; Liddle, S. T.; Mungur, S. A.; Rodden, M.; Blake, A. J.; Arnold, P. L. Chem. Commun. 2006,1124
[13] Taylor, M. D.; Carter, C. P. J. Inorg. Nucl. Chem. 1966, 24, 387
[14] Aspinall, C. H.; Tillotson, M. R. Polyhedron 1994, 73,3229
[15] Evans, W. J.; Anwander, R.; Ziller, J. W. Inorg. Chem, 1995,34,5927
[16] Cepanec, I.; Mikuldas, H.; Vinkovic, V. Synth. Commun. 2001,37,2913
[17] Li, Wan-Fei; Sun, Hong-Mei; Wang, Zhi-Guo; Chen, Mu-Zi; Shen, Qi; Zhang, Yong/. Organomet. Chem. 2005,690,6227
[18] Berich, H. P.; Roesky, W. Angew. Chem. Int. Chem., 1998,37, 1569
[19] Burgstein, M. R.; Berberich; Roesky, P. W. Chem. Eur. J., 2001, 7,14
[20] Evans, W. J.; Katsumata H. Macromolecules, 1994,27, 2330
[21] Hidenori Aihara, Tsukasa Matsuo, Hiroyuki Kawaguchi Chem. Commun. 2003, 2204
[22] Elena Mas-Marzá, Macarena Poyatos, Mercedes Sanaǘ, Eduardo Peris Organometallics, 2004, 23, 323
[23] Caddick, S.; Cloke, F.G. N.; Hitchcock, P. B.; Lewis, A. K. de K. Angew. Chem. Int. Ed. 2004, 43, 5824
[24] Rabe, G. W.; Mei, Z. P.; Riederer, F.A.; Yap, G. P. A. Inorg. Chem. 2003, 42, 3527
[25] Denise Baudry-Barbier, Nicolas Andre, Alain Dormond, Christine Pardes, Philippe Richard, Marc Visseaux, Cheng Jian Zhu Eur. J. Inorg. Chem. 1998, 1721
[26] Mario Glanz, Sebastian Dechert, Herbert Schumann, Dietmar Wolff, Jiirgen Springer Z. Anorg. Allg. Chem. 2000, 626, 2467
[27] Zhang, Li-Lu; Yao, Ying-Ming; Luo,Yun-Jie; Shen,Qi; Sun, Jie Polyhedron 2000, 19, 2243
[28] Xie, Zuowei; Chui, Kwoli; Yang, Qing-chuan; Thomas C. W. Mak, Jie Sun Organometallics 1998, 17, 3937
[29] Ling, Jun; Zhu, Wei-pu; Shen, Zhi-quan Macromolecules 2004, 37, 758
[30] 毛礼胜，浙江大学博士学位论文，1997
[31] 王志国，苏州大学博士学位论文，2006
[32] Csihony, S.; Culkin, D. A.; Sentman, A.; Dove, C. A. P.; Waymouth, R. M.; Hedrick, J. L. J. Am. Chem. Soc. 2005, 127,9079
[33] Connor, E. F.; Nyce, G. W.; Myers, M.; Mock,A.; Hedrick, J. L. J. Am. Chem. Soc. 2002, 124, 914
[34] Arnold, P. L.; Scarisbrick, A. C. Organometallics 2004, 23, 2519
[35] Arnold, P. L.; Blake, A. J.; Wilson, C. Chem. Eur. J. 2005, 11, 6095
[36] Liddle, S. T.; Arnold, P. L. Organometallics 2005, 24, 2597
[37] Cheng, L.; Yang, Y. H.; Luo, M. R.; Zhang, D. R. Inorg. Chim. Acta 1987, 130, 125
[38] Babai, A.; Mudring, A. V. Inorg. Chem. 2005, 44, 8168
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