Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Addition of gaseous CO 2 to solutions of bis(π-η 5:σ-η 1 -pentafulvene)titanium complexes results in the selective insertion reaction of one equivalent of O═C═O into one of the two frustrated Ti–C exo bonds under mild conditions. The formation of κ 1 O - and κ 2 O, O -carboxylate titanium complexes is observed and characterized by single crystal X-ray analysis, NMR and IR spectroscopy. The nature of Ti–O interactions is established by computational studies. The reactivity of the remaining pentafulvene ligand is demonstrated in reactions with H-acidic and multiple-bond-containing substrates. The reactions with etheric HCl results in the selective formation of Ti–Cl complexes by protonation of the second pentafulvene moiety, disregarding the carboxylate ligand. The formed chlorido complexes are used in follow-up reactions with methyllithium, resulting in the methylation of the complexes via salt metathesis reactions, and reduction of the chloride complexes with sodium amalgam results in the formation of dimeric κ 1 O -μ- O /bridged-carboxylate Ti (III) complexes.
Source: Organometallics
Institution: Carl von Ossietzky Universität Oldenburg
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
SDG: Climate action
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W4409101520