Complex (PNP)TiCHtBu(CH2tBu) (PNP - = N[2-P(CHMe2)2-4-methylphenyl]2) eliminates H3CtBu to form transient (PNP)TiC tBu, which activates the C-F bond of ortho-difluoropyridine and ortho-fluoropyridine to form the alkylidene-fluoride complexes, (PNP)TiC[ tBu(NC5H3F)](F) (1) and (PNP)TiC[ tBu(NC5H4)](F) (2), respectively. When (PNP)TiCHtBu(CH2tBu) is treated with meta-fluoropyridine, the ring-opened product (PNP)Ti(C(tBu)CC 4H3-3-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/β-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/β-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.
ASJC Scopus subject areas
- Inorganic Chemistry