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题名: 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
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
发表日期: 2013
DOI: 10.1039/c3dt32570a
卷: 42, 期:12, 页:4163-4174
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Inorganic & Nuclear
研究领域[WOS]: Chemistry
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.
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
语种: 英语
WOS记录号: WOS:000315351800009
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/137483
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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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

Recommended Citation:
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.
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