ja5b11365_si_001.cif (35.57 kB)
A Model of a Closed Cycle of Water Splitting Using ansa-Titanocene(III/IV) Triflate Complexes
dataset
posted on 2015-12-30, 00:00 authored by Christian Godemann, Dirk Hollmann, Monty Kessler, Haijun Jiao, Anke Spannenberg, Angelika Brückner, Torsten BeweriesA series of ansa-titanocene triflate complexes
are described as model compounds for the elementary steps of light-driven
overall water splitting. Titanocene(III) triflate complexes are readily
obtained by reaction of a titanocene source with Yb(OTf)3. Subsequent reactions with water and with/without TEMPO as hydrogen
scavenger are studied. The as-obtained titanocene(IV) compounds can
be photoreduced to give titanocene(III) triflate complexes, which
can undergo further hydrolysis to form a closed catalytic cycle of
water splitting. No further degradation of the photoreduced species
was observed because of the presence of the OTf group. The stability
of the system was evaluated in an experiment with high concentrations
of water and TEMPO. X-ray crystallography on all titanocene complexes,
EPR and NMR spectroscopy, and DFT were used to support our observations.
