Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Chemoselective Hydrogenation of Nitroarenes Catalyzed by Molybdenum Sulphide Clusters. / Pedrajas, Elena; Sorribes, Iván; Gushchin, Artem L. и др.
в: ChemCatChem, Том 9, № 6, 20.03.2017, стр. 1128-1134.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Chemoselective Hydrogenation of Nitroarenes Catalyzed by Molybdenum Sulphide Clusters
AU - Pedrajas, Elena
AU - Sorribes, Iván
AU - Gushchin, Artem L.
AU - Laricheva, Yuliya A.
AU - Junge, Kathrin
AU - Beller, Matthias
AU - Llusar, Rosa
N1 - Publisher Copyright: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/3/20
Y1 - 2017/3/20
N2 - Herein, we describe an atom efficient and general protocol for the chemoselective hydrogenation of nitroarenes to anilines catalyzed by well-defined diimino and diamino cubane-type Mo3S4 clusters. The novel diimino [Mo3S4Cl3(dnbpy)3]+ ([5]+) (dnbpy=4,4′-dinonyl-2,2′-dipyridyl, L1) trinuclear complex was synthesized in high yields by simple ligand substitution reactions starting from the thiourea (tu) [Mo3S4(tu)8(H2O)]Cl4⋅4 H2O (3) precursor. This strategy has also been successfully adapted for the isolation of the diamino [Mo3S4Cl3(dmen)3](BF4) ([6](BF4)), (dmen=N,N′-dimethylethylenediamine) salt. Applying these catalysts, high selectivity in the hydrogenation of functionalized nitroarenes has been accomplished. Over thirty anilines bearing synthetically functional groups have been synthesized in 70 to 99 % yield. Notably, the integrity of the cluster core is preserved during catalysis. Based on kinetic studies on the hydrogenation of nitrobenzene and other potential reaction intermediates, the direct reduction to aniline is the preferential route.
AB - Herein, we describe an atom efficient and general protocol for the chemoselective hydrogenation of nitroarenes to anilines catalyzed by well-defined diimino and diamino cubane-type Mo3S4 clusters. The novel diimino [Mo3S4Cl3(dnbpy)3]+ ([5]+) (dnbpy=4,4′-dinonyl-2,2′-dipyridyl, L1) trinuclear complex was synthesized in high yields by simple ligand substitution reactions starting from the thiourea (tu) [Mo3S4(tu)8(H2O)]Cl4⋅4 H2O (3) precursor. This strategy has also been successfully adapted for the isolation of the diamino [Mo3S4Cl3(dmen)3](BF4) ([6](BF4)), (dmen=N,N′-dimethylethylenediamine) salt. Applying these catalysts, high selectivity in the hydrogenation of functionalized nitroarenes has been accomplished. Over thirty anilines bearing synthetically functional groups have been synthesized in 70 to 99 % yield. Notably, the integrity of the cluster core is preserved during catalysis. Based on kinetic studies on the hydrogenation of nitrobenzene and other potential reaction intermediates, the direct reduction to aniline is the preferential route.
KW - anilines
KW - clusters
KW - hydrogenation
KW - molybdenum
KW - nitroarenes
KW - sulfides
KW - COMPLEXES
KW - IRON
KW - DISULFIDE
KW - HOMOGENEOUS HYDROGENATION
KW - MILD
KW - NANOPARTICLES
KW - SELECTIVE HYDROGENATION
KW - REDUCTION
KW - NITRO-COMPOUNDS
KW - METAL
UR - http://www.scopus.com/inward/record.url?scp=85013433882&partnerID=8YFLogxK
U2 - 10.1002/cctc.201601496
DO - 10.1002/cctc.201601496
M3 - Article
AN - SCOPUS:85013433882
VL - 9
SP - 1128
EP - 1134
JO - ChemCatChem
JF - ChemCatChem
SN - 1867-3880
IS - 6
ER -
ID: 9048591