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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
Fan, Hongjun1; Fout, Alison R.2,3; Bailey, Brad C.2,3; Pink, Maren2,3; Baik, Mu-Hyun2,3; Mindiola, Daniel J.2,3
Source PublicationDALTON TRANSACTIONS
2013
DOI10.1039/c3dt32570a
Volume42Issue:12Pages:4163-4174
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Inorganic & Nuclear
WOS Research AreaChemistry
WOS KeywordTUNGSTEN 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
AbstractComplex (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.
Language英语
WOS IDWOS:000315351800009
Citation statistics
Cited Times:10[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/137483
Collection中国科学院大连化学物理研究所
Affiliation1.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
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.
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