A Homogeneous System for the Photogeneration of Hydrogen from Water Based on a Platinum(II) Terpyridyl Acetylide Chromophore and a Molecular Cobalt Catalyst

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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 × 109 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 < 7 and pH > 12. Irradiation of the reaction solution initially containing 1.61 × 10−2 M TEOA, 1.11 × 10−5 M of 3, and 1.99 × 10−4 M of Co catalyst 1 in MeCN/water (3:2 v/v) at pH = 8.5 for 10 h with λ > 410 nm yields 400 turnovers of H2. When TEOA is 0.27 M, ∼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.

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