Mechanistic insight into proton-coupled mixed valency. Issue 1 (26th October 2015)

• Record Type: Journal Article
• Authors: Wilkinson, Luke A.; Vincent, Kevin B.; Meijer, Anthony J. H. M.; Patmore, Nathan J.
• Is Part Of: Chemical communications. Volume 52:Issue 1(2015)
• Page Start: 100
• Page End: 103
• Publication Date: 2015-10-26
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c5cc07101a
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : Stabilisation of the mixed-valence state in [Mo2 (TiPB)3 (HDOP)]2 + (HTiPB = 2, 4, 6-triisopropylbenzoic acid, H2 DOP = 3, 6-dihydroxypyridazine) by electron transfer (ET) is related to the proton coordinate of the bridging ligands. Abstract : Stabilisation of the mixed-valence state in [Mo2 (TiPB)3 (HDOP)]2 + (HTiPB = 2, 4, 6-triisopropylbenzoic acid, H2 DOP = 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.