Understanding intermolecular C-F bond activation by a transient titanium neopentylidyne: experimental and theoretical studies on the competition between 1,2-CF bond addition and [2+2]-cycloaddition/beta-fluoride elimination
文献类型：期刊论文
| 作者 | Fan, Hongjun1; Fout, Alison R.2,3; Bailey, Brad C.2,3; Pink, Maren2,3; Baik, Mu-Hyun2,3; Mindiola, Daniel J.2,3 |
| 刊名 | dalton transactions
 |
| 出版日期 | 2013 |
| 卷号 | 42期号:12页码:4163-4174 |
| 英文摘要 | complex (pnp)ti=(chbu)-bu-t((ch2bu)-bu-t) (pnp- = n[2-p(chme2)(2)-4-methylphenyl](2)) eliminates (h3cbu)-bu-t to form transient (pnp)ti (cbu)-bu-t, which activates the c-f bond of ortho-difluoropyridine and ortho-fluoropyridine to form the alkylidene-fluoride complexes, (pnp)ti=c[bu-t(nc5h3f)](f) (1) and (pnp)ti=c[bu-t(nc5h4)](f) (2), respectively. when (pnp)ti=(chbu)-bu-t((ch2bu)-bu-t) is treated with meta-fluoropyridine, the ring-opened product (pnp)ti(c(bu-t)cc4h3-3-fnh) (3) is the only recognizable titanium metal complex formed. theoretical studies reveal that pyridine binding disfavors 1,2-cf bond addition across the alkylidyne ligand in the case of ortho-fluoride pyridines, while sequential [2 + 2]-cycloaddition/beta-fluoride elimination is a lower energy pathway. in the case of meta-fluoropyridine, [2 + 2]-cycloaddition and subsequent ring-opening metathesis is favored as opposed to c-h bond addition or sequential [2 + 2]-cycloaddition/beta-hydride elimination. in all cases, c-h bond addition of ortho-fluoropyridines or meta-fluoropyridine is discouraged because such substrate must bind to titanium via its c-h bond, which is rather weak compared to the titanium-pyridine binding. |
| WOS标题词 | science & technology ; physical sciences |
| 类目[WOS] | chemistry, inorganic & nuclear |
| 研究领域[WOS] | chemistry |
| 关键词[WOS] | tungsten alkylidene complexes ; effective core potentials ; ring-opening metathesis ; solvation free-energies ; h activation ; hydrocarbon activation ; molecular calculations ; metal-complexes ; reversible 1,2-rh-elimination ; thermal-activation |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000315351800009 |
| 公开日期 | 2015-11-10 |
| 源URL | [http://159.226.238.44/handle/321008/137483]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 作者单位 | 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian, Peoples R China 2.Indiana Univ, Dept Chem, Ctr Mol Struct, Bloomington, IN 47405 USA 3.Indiana Univ, Sch Informat, Bloomington, IN 47405 USA |
| 推荐引用方式 GB/T 7714 | Fan, Hongjun,Fout, Alison R.,Bailey, Brad C.,et al. Understanding intermolecular C-F bond activation by a transient titanium neopentylidyne: experimental and theoretical studies on the competition between 1,2-CF bond addition and [2+2]-cycloaddition/beta-fluoride elimination[J]. dalton transactions,2013,42(12):4163-4174. |
| APA | Fan, Hongjun,Fout, Alison R.,Bailey, Brad C.,Pink, Maren,Baik, Mu-Hyun,&Mindiola, Daniel J..(2013).Understanding intermolecular C-F bond activation by a transient titanium neopentylidyne: experimental and theoretical studies on the competition between 1,2-CF bond addition and [2+2]-cycloaddition/beta-fluoride elimination.dalton transactions,42(12),4163-4174. |
| MLA | Fan, Hongjun,et al."Understanding intermolecular C-F bond activation by a transient titanium neopentylidyne: experimental and theoretical studies on the competition between 1,2-CF bond addition and [2+2]-cycloaddition/beta-fluoride elimination".dalton transactions 42.12(2013):4163-4174. |
入库方式： OAI收割
来源：大连化学物理研究所
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