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Synthesis of [Bis(hexamethylene)cyclopentadienone]iron Tricarbonyl and its Application to the Catalytic Reduction of C=O Bonds
Author(s) -
Vailati Facchini Sofia,
Neudörfl JörgMartin,
Pignataro Luca,
Cettolin Mattia,
Gennari Cesare,
Berkessel Albrecht,
Piarulli Umberto
Publication year - 2017
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201601591
Subject(s) - chemistry , catalysis , reactivity (psychology) , carbonylation , yield (engineering) , medicinal chemistry , crystal structure , kinetics , transfer hydrogenation , organic chemistry , carbon monoxide , materials science , medicine , alternative medicine , physics , pathology , quantum mechanics , metallurgy , ruthenium
Herein, we report the synthesis of [bis(hexamethylene)cyclopentadienone]iron tricarbonyl ( 1 b ) by the reaction of cyclooctyne with Fe(CO) 5 and the investigation of its catalytic properties in C=O bond reduction. As a result of the peculiar reactivity of cyclooctyne, 1 b was formed in good yield (56 %) by intermolecular cyclative carbonylation/complexation with Fe(CO) 5 . Compound 1 b was characterized fully and its crystal structure was determined by using XRD. Catalytic tests revealed that, upon in situ activation with Me 3 NO, 1 b promotes the hydrogenation of ketones, aldehydes, and activated esters as well as the transfer hydrogenation of ketones and shows a higher activity than the classical “Knölker complex” ( 1 a ). Studies on the hydrogenation kinetics in the presence of 1 a and 1 b (respectively) suggest that this difference in activity is probably caused by the better stability of the 1 b ‐derived complex than that of the in situ generated Knölker–Casey catalyst.