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Copper(I) in the Cleft: Syntheses, Structures and Catalytic Properties of {Cu + –Co 3+ –Cu + } and {Cu + –Fe 3+ –Cu + } Heterobimetallic Complexes
Author(s) -
Singh Amit Pratap,
Gupta Rajeev
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000547
Subject(s) - chemistry , copper , catalysis , crystallography , pyridine , molecule , crystal structure , phenols , inorganic chemistry , redox , oxidation state , oxygen , stereochemistry , medicinal chemistry , organic chemistry
The present work demonstrates the synthesis and characterization of {Cu + –Co 3+ –Cu + } and {Cu + –Fe 3+ –Cu + } heterobimetallic complexes utilizing Co 3+ and Fe 3+ coordination complexes as the building blocks. The crystallographic investigation of the {Cu + –Co 3+ –Cu + } and {Cu + –Fe 3+ –Cu + } heterometallic complexes reveal that the Cu I ions in the clefts are coordinated by two pyridine nitrogen atoms and one CH 3 CN molecule. The crystal structures also show several weak interactions that result in interesting packing in the solid state. The accessible Cu 2+/+ redox potential and presence of labile site on the copper center has been utilized for the oxidation of hindered phenols in the presence of molecular oxygen. Hindered phenols were oxidized to the C–C‐coupled products in most cases, however, de‐alkylation resulted in the case of 2,4,6‐trisubstituted phenols. Interestingly, when H 2 O 2 was used as oxidant, de‐alkylation was not observed; suggesting the uniqueness of the active species generated in the presence of catalyst and molecular oxygen.