Lutetium-Methanediide-Alkyl Complexes: Synthesis and Chemistry
文献类型：期刊论文
| 作者 | Li, Shihui1; Wang, Meiyan2; Liu, Bo3; Li, Lei1; Cheng, Jianhua1; Wu, Chunji1; Liu, Dongtao1; Liu, Jingyao2; Cui, Dongmei1 |
| 刊名 | CHEMISTRY-A EUROPEAN JOURNAL
 |
| 出版日期 | 2014-11-17 |
| 卷号 | 20期号:47页码:15493-15498 |
| 关键词 | Binuclear Isocyanate Isocyanide Lanthanide Methanediide |
| ISSN号 | 0947-6539 |
| DOI | 10.1002/chem.201404809 |
| 英文摘要 | The first four-coordinate methanediide/alkyl lutetium complex (BODDI) Lu-2(CH2SiMe3)(2)(mu(2)-CHSiMe3)(THF)(2) (BODDI=ArNC(Me) CHCOCHC(Me) NAr, Ar=2,6-iPr(2)C(6)H(3)) (1) was synthesized by a thermolysis methodology through a-H abstraction from a Lu-CH2SiMe3 group. Complex 1 reacted with equimolar(2),6-iPrC(6)H(3)NH(2) and Ph2C=O to give the corresponding lutetium bridging imido and oxo complexes (BODDI) Lu-2(CH2SiMe3)(2)(mu(2)-N-2,6-iPr(2)C(6)H(3))(THF)(2) (2) and (BODDI) Lu-2(CH2SiMe3)(2)(mu(2)-O)(THF)(2) (3). Treatment of 3 with Ph2C=O (4 equiv) caused a rare insertion of Lu-mu(2)-O bond into the C=O group to afford a diphenylmethyl diolate complex 4. Reaction of 1 with PhN=C=O (2 equiv) led to the migration of SiMe3 to the amido nitrogen atom to give complex (BODDI) Lu-2(CH2SiMe3)(2)-mu-{PhNC(O)CHC(O)NPh(SiMe3)kappa N-3,O,O}(THF) (5). Reaction of 1 with tBuN equivalent to C formed an unprecedented product (BODDI) Lu-2(CH2SiMe3){mu(2)-[eta(2):eta(2)-tBuNC(=CH2) SiMe2CHC=NtBu-k 1N]}(tBuN equivalent to C)(2) (6) through a cascade reaction of N equivalent to C bond insertion, sequential cyclometalative gamma-(sp(3))-H activation, C equivalent to C bond formation, and rearrangement of the newly formed carbene intermediate. The possible mechanistic pathways between 1, PhN=C=O, and tBuN equivalent to C were elucidated by DFT calculations. |
| 语种 | 英语 |
| WOS记录号 | WOS:000345234800030 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/51441]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Cui, Dongmei |
| 作者单位 | 1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Jilin Univ, Inst Theoret Chem, State Key Lab Theoret & Computat Chem, Changchun 130022, Peoples R China 3.Jilin Univ, Key Lab Automobile Mat, Minist Educ, Dept Mat Sci & Engn, Changchun 130025, Peoples R China |
| 推荐引用方式 GB/T 7714 | Li, Shihui,Wang, Meiyan,Liu, Bo,et al. Lutetium-Methanediide-Alkyl Complexes: Synthesis and Chemistry[J]. CHEMISTRY-A EUROPEAN JOURNAL,2014,20(47):15493-15498. |
| APA | Li, Shihui.,Wang, Meiyan.,Liu, Bo.,Li, Lei.,Cheng, Jianhua.,...&Cui, Dongmei.(2014).Lutetium-Methanediide-Alkyl Complexes: Synthesis and Chemistry.CHEMISTRY-A EUROPEAN JOURNAL,20(47),15493-15498. |
| MLA | Li, Shihui,et al."Lutetium-Methanediide-Alkyl Complexes: Synthesis and Chemistry".CHEMISTRY-A EUROPEAN JOURNAL 20.47(2014):15493-15498. |
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来源：化学研究所
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