A Homogeneous System for the Photogeneration of Hydrogen from Water Based on a Platinum(II) Terpyridyl Acetylide Chromophore and a Molecular Cobalt Catalyst
Citations Over TimeTop 1% of 2008 papers
Abstract
The complex [Co(dmgH)2pyCl]2+ (1, dmgH = dimethylglyoximate, py = pridine) has been used as a molecular catalyst for visible light driven hydrogen production in the presence of [Pt(tolylterpyridine)(phenylacetylide)]+ (3) as a photosensitizer and triethanolamine (TEOA) as a sacrificial reducing agent. Complex 3 is quenched oxidatively by [Co(dmgH)pyCl]2+ (1) with a rate constant kq of 1.27 x 10(9) M(-1) s(-1). Photogeneration of H2 is only seen when 1 + 3 + TEOA are all present. H2 production is maximized for this system at pH 8.5 and declines to very low levels at pH 12. Irradiation of the reaction solution initially containing 1.61 x 10(-2) M TEOA, 1.11 x 10(-5) M of 3, and 1.99 x 10(-4) M of Co catalyst 1 in MeCN/water (3:2 v/v) at pH = 8.5 for 10 h with lambda > 410 nm yields 400 turnovers of H2. When TEOA is 0.27 M, approximately 1000 turnovers are obtained after 10 h of irradiation. Spectroscopic study of the photolyses solutions suggests that H2 formation proceeds via Co(I) and protonation to form Co(III) hydride species.
Related Papers
- → Synthesis and characterisation of mono-acetylide and unsymmetrical bis-acetylide complexes of ruthenium and osmium: X-ray structure determinations on [(dppe)2Ru(Cl)(CC–C6H4-p-NO2)], [(dppe)2Ru(Cl)(CC–C6H3-o-CH3-p-NO2)] and [(dppm)2Os(CC–C6H4-p-CH3)(CC–C6H4-p-NO2)](1999)59 cited
- → Organometallic complexes for non-linear optics VII. Cubic optical non-linearities of octahedral trans-bis{bis(diphenylphosphino)methane}ruthenium acetylide complexes; X-ray crystal structure of trans-[Ru(CCPH)(4-CCC6H4NO2)(dppm)2](1996)62 cited
- → Single Oligomer Spectra Probe Chromophore Nanoenvironments of Tetrameric Fluorescent Proteins(2006)20 cited
- → Mixed Metal Acetylide Complexes(2007)19 cited
- → ChemInform Abstract: Syntheses and Reactivity of Acetylide‐Containing Clusters of Group 1B Metals. Stepwise Syntheses of Trinuclear (Au2Cu(C2Ph)4)‐ and Pentanuclear (Au3Cu2(C2Ph)6)‐ and (Au3Ag2(C2Ph)6)‐ Clusters.(1988)