Catalysis Science & Technology
Page 4 of 5
DOI: 10.1039/C8CY01480A
University of Technology, No. 391 Binshuixi Road, Tianjin 300384, P. R.
China. Fax: (+)86-22-60214259; Tel: (+86)-22-6024259;
E-mail: tongxinli@tju.edu.cn; tongxli@sohu.com (X. T.) or
wanjuntjlg@sina.com (J. W.).
45 † Electronic Supplementary Information (ESI) available: [Experiment
such as catalyst preparation and characterization, the GC and GCꢀMS
spectra of the product and several results for optiumization of conditions].
See DOI: 10.1039/b000000x/
been confirmed by previous researches which refer that Zr(IV)
Zr(IV) tends to coordinate with the amide to form Zr(IV)ꢀO and
Zr(IV)ꢀN,28 which promotes the decomposition of the amide.29, 30
Also, our experimental data further indicated that, owing to the
existence of the bridging hydroxyl ZrꢀOH groups, ZrO(OH)2 or
Zr(OH)4 exhibited higher catalytic activity than ZrO2 in the
decomposition of amide; therefore, the activated hydroxyl group
plays an important role during the coordination of Zr(IV) with
amide. The next step is the condensation of aromatic aldehyde
5
‡ Footnotes should appear here. These might include comments relevant
50 to but not central to the matter under discussion, limited experimental and
spectral data, and crystallographic data.
10 and dimethyl amine to the iminium cation as the intermediate.
Then, the formed iminium cation intermediate is further reduced
by in situ generated formic acid to obtain the tertiary amines.
Herein, the continued consumption of formic acid and
dimethylamine further push the equilibrium of the DMF
15 descomposition reaction to the right. It can be concluded that the
coordination property of Zr(IV), rich bridging hydroxyl groups
and high specific surface area of ZrO(OH)2 or Zr(OH)4 should be
crucial factors to promote the occurrence of reductive amination.
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Acknowledgement
We are grateful for the support of the National Natural Science
Foundation of China (No. 21878235), Tianjin Program of
35 Application Foundation and Advanced Technology (No.
17JCYBJC20200) and the State Key Program of National Natural
Science Foundation of China (No. 21336008).
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Notes and references
a Tianjin Key Laboratory of Organic Solar Cells and Photochemical
40 Conversion, School of Chemistry and Chemical Engineering, Tianjin
4
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