posted on 2018-07-25, 14:11authored byJiaoyan Li, Yingmiao Ma, Zheng Wang, Qingbin Liu, Gregory A. Solan, Yanping Ma, Wen-Hua Sun
Reaction of 8-amino-5,6,7,8-tetrahydroquinoline with RuCl2(PPh3)3 at room temperature affords the ruthenium(ii) chelate (8-NH2-C9H10N)RuCl2(PPh3)2 (E), in which the two triphenylphosphine ligands are disposed mutually cis. By contrast, when the reaction is performed at reflux ligand oxidation/dehydrogenation occurs along with cis-trans reorganization of the triphenylphosphines to form the 8-imino-5,6,7-trihydroquinoline-ruthenium(ii) complex, (8-NH-C9H9N)RuCl2(PPh3)2 (F). Complex F can also be obtained in higher yield by heating a solution of E alone to reflux. Comparison of their molecular structures highlights the superior binding properties of the bidentate imine ligand in F over its amine-containing counterpart in E. Both complexes are highly effective in the transfer hydrogenation of a wide range of alkyl-, aryl- and cycloalkyl-containing ketones affording their corresponding secondary alcohols with loadings of as low as 0.1 mol%. Significantly, F can deliver excellent conversions even in bench quality 2-propanol in reaction vessels open to the air, whereas the catalytic efficiency of E is diminished by the presence of air but only operates efficiently under inert conditions.
Funding
This work is supported by the National Natural Science
Foundation of China (No. 21476060, and U1362204) and
the Nature Science Foundation of Hebei Province
(No. B2014205049), China. G. A. S. thanks the Chinese
Academy of Sciences for a President’s International Fellowship
for Visiting Scientists.
History
Citation
Dalton Transactions, 2018, 47 (26), pp. 8738-8745
Author affiliation
/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry
Electronic supplementary information (ESI) available: Figures, tables, and
giving NMR spectra of the new complexes and a selected substrate. CCDC
1586459 for E, 1586458 for F. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/c8dt01919c;The file associated with this record is under embargo until 12 months after publication, in accordance with the publisher's self-archiving policy. The full text may be available through the publisher links provided above.