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Generation of Powerful Tungsten Reductants by Visible Light Excitation

Sattler, Wesley and Ener, Maraia E. and Blakemore, James D. and Rachford, Aaron D. and LaBeaume, Paul J. and Thackeray, James W. and Cameron, James F. and Winkler, Jay R. and Gray, Harry B. (2013) Generation of Powerful Tungsten Reductants by Visible Light Excitation. Journal of the American Chemical Society, 135 (29). pp. 10614-10617. ISSN 0002-7863. doi:10.1021/ja4047119.

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The homoleptic arylisocyanide tungsten complexes, W(CNXy)_6 and W(CNIph)_6 (Xy = 2,6-dimethylphenyl, Iph = 2,6-diisopropylphenyl), display intense metal to ligand charge transfer (MLCT) absorptions in the visible region (400–550 nm). MLCT emission (λ_max ≈ 580 nm) in tetrahydrofuran (THF) solution at rt is observed for W(CNXy)6 and W(CNIph)_6 with lifetimes of 17 and 73 ns, respectively. Diffusion-controlled energy transfer from electronically excited W(CNIph)_6 (*W) to the lowest energy triplet excited state of anthracene (anth) is the dominant quenching pathway in THF solution. Introduction of tetrabutylammonium hexafluorophosphate, [Bun4N][PF_6], to the THF solution promotes formation of electron transfer (ET) quenching products, [W(CNIph)6]+ and [anth]^•–. ET from *W to benzophenone and cobalticenium also is observed in [Bun4N][PF6]/THF solutions. The estimated reduction potential for the [W(CNIph)6]^(+)/*W couple is −2.8 V vs Cp_(2)Fe^(+/0), establishing W(CNIph)_6 as one of the most powerful photoreductants that has been generated with visible light.

Item Type:Article
Related URLs:
URLURL TypeDescription
Sattler, Wesley0000-0001-5316-260X
Blakemore, James D.0000-0003-4172-7460
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2013 American Chemical Society. Received: May 10, 2013; Published: July 15, 2013. Dedicated to the memory of Nicholas J. Turro. The authors thank Jeffrey J. Warren, James R. McKone, and Oliver S. Shafaat for helpful discussions. Our work is supported by the National Science Foundation Center for Chemical Innovation in Solar Fuels (CHE-0802907); CCI postdoctoral fellowship to W.S.; and the Dow Chemical Company through the university partnership program (Agreement No. 227027AH).
Group:CCI Solar Fuels
Funding AgencyGrant Number
NSF Postdoctoral FellowshipUNSPECIFIED
Dow Chemical Company227027AH
Issue or Number:29
Record Number:CaltechAUTHORS:20131008-104014521
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Official Citation:Generation of Powerful Tungsten Reductants by Visible Light Excitation Wesley Sattler, Maraia E. Ener, James D. Blakemore, Aaron A. Rachford, Paul J. LaBeaume, James W. Thackeray, James F. Cameron, Jay R. Winkler, and Harry B. Gray Journal of the American Chemical Society 2013 135 (29), 10614-10617
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:41736
Deposited On:10 Oct 2013 19:39
Last Modified:10 Nov 2021 04:33

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