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DOI: 10.1039/A607058B (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1019-1024

Photochemistry of [Re(bipy)(CO)3(PPh3)]+ (bipy = 2,2′-bipyridine) in the presence of triethanolamine associated with photoreductive fixation of carbon dioxide: participation of a chain reaction mechanism

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Hisao Hori, Frank P. A. Johnson, Kazuhide Koike, Koji Takeuchi, Takashi Ibusuki and Osamu Ishitani

Abstract

The complex fac-[Re(bipy)(CO)3(PPh3)]+1+ (bipy = 2,2′-bipyridine) was converted into a formate complex fac-[Re(bipy)(CO)3{OC(O)H}] 2 in a 52.2% yield by irradiation in the presence of triethanolamine (teoa) and CO2. This photochemical fixation of CO2 proceeds via a unique reaction mechanism: (i[hair space]) irradiation of 1+ in teoa–dimethylformamide (dmf[hair space]) resulted in the efficient formation of fac-[Re(bipy)(CO)3(teoa)]+3+ and fac-[Re(bipy)(CO)3(dmf[hair space])]+4+ in a quantum yield of 16.9; (ii[hair space]) the ligand substitution was explained in terms of a chain mechanism involving an initial electron transfer from teoa to excited 1+, followed by substitution of the PPh3 ligand of 1 with teoa and dmf to give 3 and 4; subsequent electron exchange of 3 and 4 with 1+ leads to the formation of 3+ and 4+ accompanied by the regeneration of 1; (iii[hair space]) the formate complex 2 was formed in a quantum yield of 1.1 × 10-3 upon excitation of 3+ and 4+ in the presence of CO2; (iv) further irradiation after the formation of 2 resulted in the photocatalytic reduction of CO2 to CO in a quantum yield of 0.05.

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