In:
Angewandte Chemie, Wiley, Vol. 135, No. 30 ( 2023-07-24)
Abstract:
Photocatalytic 2‐iodoethanol (IEO) coupling provides 1,4‐butanediol (BDO) of particular interest to produce degradable polyesters. However, the reduction potential of IEO is too negative (−1.9 vs NHE) to be satisfied by most of the semiconductors, and the kinetics of transferring one electron for IEO coupling is slow. Here we design a catalytic Ni complex, which works synergistically with TiO 2 , realizing reductive coupling of IEO powered by photo‐energy. Coordinating by terpyridine stabilizes Ni 2+ from being photo‐deposited to TiO 2 , thereby retaining the steric configuration beneficial for IEO coupling. The Ni complex can rapidly extract electrons from TiO 2 , generating a low‐valent Ni capable of reducing IEO. The photocatalytic IEO coupling thus provides BDO in 72 % selectivity. By a stepwise procedure, BDO is obtained with 70 % selectivity from ethylene glycol. This work put forward a strategy for the photocatalytic reduction of molecules requiring strong negative potential.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v135.30
DOI:
10.1002/ange.202301668
Language:
English
Publisher:
Wiley
Publication Date:
2023
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505872-7
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1479266-7
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