Mechanistic insight into proton-coupled mixed valency.
Stabilisation of the mixed-valence state in [Mo2(TiPB)3(HDOP)]2(+) (HTiPB = 2,4,6-triisopropylbenzoic acid, H2DOP = 3,6-dihydroxypyridazine) by electron transfer (ET) is related to the proton coordinate of the bridging ligands. Spectroelectrochemical studies suggest that ET is slower than 10(9) s(-1). The mechanism has been probed using DFT calculations, which show that proton transfer induces a larger dipole in the molecule resulting in ET.
Department of Chemical Sciences, University of Huddersfield, Huddersfield HD1 3DH, UK. n.j.patmore@hud.ac.uk and Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK.
Luke A
LA
Wilkinson
Department of Chemical Sciences, University of Huddersfield, Huddersfield HD1 3DH, UK. n.j.patmore@hud.ac.uk.
Kevin B
KB
Vincent
Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK.
Anthony J H M
AJ
Meijer
Department of Chemical Sciences, University of Huddersfield, Huddersfield HD1 3DH, UK. n.j.patmore@hud.ac.uk.
Nathan J
NJ
Patmore