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. 2020 May 25;11(25):6370-6382.
doi: 10.1039/d0sc01340d. eCollection 2020 Jul 7.

Luminescent tungsten(vi) complexes as photocatalysts for light-driven C-C and C-B bond formation reactions

Daohong Yu  1   2 , Wai-Pong To  2 , Glenna So Ming Tong  2 , Liang-Liang Wu  2 , Kaai-Tung Chan  2 , Lili Du  2 , David Lee Phillips  2 , Yungen Liu  1 , Chi-Ming Che  1   2   3
Affiliations

Luminescent tungsten(vi) complexes as photocatalysts for light-driven C-C and C-B bond formation reactions

Daohong Yu et al. Chem Sci. .

Abstract

The realization of photocatalysis for practical synthetic application hinges on the development of inexpensive photocatalysts which can be prepared on a large scale. Herein an air-stable, visible-light-absorbing photoluminescent tungsten(vi) complex which can be conveniently prepared at the gram-scale is described. This complex could catalyse photochemical organic transformation reactions including borylation of aryl halides, such as aryl chloride, reductive coupling of benzyl bromides for C-C bond formation, reductive coupling of phenacyl bromides, and decarboxylative coupling of redox-active esters of alkyl carboxylic acid with high product yields and broad functional group tolerance.

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Figures

Fig. 1
Fig. 1. Tungsten(vi) complexes W1a–W1c studied in this work.
Fig. 2
Fig. 2. UV-vis absorption (solid line) and emission (dashed line) spectra of W1a–W1c in degassed dichloromethane solutions at room temperature.
Fig. 3
Fig. 3. Emission spectra of (a) W1b and (b) W1c in CH2Cl2 under aerated conditions and under N2.
Fig. 4
Fig. 4. (a) Femtosecond time-resolved emission spectra of W1a in CH2Cl2 and (b) emission of W1a in different solvents (adapted with permission from ref. 15. Copyright 2019, Wiley-VCH Verlag GmbH & Co. KGaA).
Fig. 5
Fig. 5. Transition dipole moment density (left) and the fragment transition dipole moment (right) along the z-direction of the S0 → S1 excitation in toluene solution at the respective optimized S0 geometries of W1c (top) and W1a (bottom). Colour code: magenta, negative; green, positive; isovalue = 0.001 a.u.
Fig. 6
Fig. 6. fs-TA spectra of (a) W1a and (b) W1b in CH2Cl2 at room temperature.
Scheme 1
Scheme 1. Photo-induced dehydrogenation reactions catalysed by W1a.
Fig. 7
Fig. 7. Nanosecond time-resolved absorption difference spectra of (left) W1a only and (right) W1a in the presence of N,N-diisopropylethylamine (0.02 M) in degassed CH3CN at room temperature.
See this image and copyright information in PMC

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