3 years ago

The Femtochemistry of a Ferracyclobutadiene

The Femtochemistry of a Ferracyclobutadiene
Alexander C. Filippou, Ujjal Das, Peter Vöhringer, Boris Wezisla, Jörg Lindner
The eminent role of metallacyclobutadienes as catalytic intermediates in organic synthesis and polymer chemistry is widely acknowledged. In contrast, their photochemistry is as yet entirely unexplored. Herein, the photo-induced primary processes of a ferracyclobutadiene tricarbonyl complex in solution are revealed by femtosecond mid-infrared spectroscopy. The time-resolved vibrational spectra expose an ultrafast substitution of a basal CO ligand by a solvent molecule in a consecutive dissociation–association mechanism. Following optical excitation, the system relaxes non-radiatively to the triplet ground state from which a CO is expelled. Since the triplet state is bound with respect to Fe−CO cleavage, the dissociation can only occur from vibrationally excited states. The excitation energy, vibrational relaxation, and intersystem crossing to the singlet ground state control the primary quantum yield for formation of the ferracyclic dicarbonyl–solvent product complex. Blink and you'll miss it: Femtosecond infrared spectroscopy was used to monitor the photochemical dynamics of an electron-rich, puckered ferracyclobutadiene in liquid solution. The results show an ultrafast substitution of a CO ligand by a solvent molecule.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702987

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