Premium
K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation
Author(s) -
Lum June S.,
Tahsini Laleh,
Golen James A.,
Moore Curtis,
Rheingold Arnold L.,
Doerrer Linda H.
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201204275
Subject(s) - chemistry , reactivity (psychology) , alkoxide , medicinal chemistry , copper , valence (chemistry) , inorganic chemistry , counterion , adduct , intramolecular force , crystallography , nucleophile , aryl , stereochemistry , alkyl , ion , organic chemistry , catalysis , medicine , alternative medicine , pathology
Seven E[Cu(OR) 2 ] copper(I) complexes (E=K + , {K(18C6)} + (18C6=[18]crown‐6), or Ph 4 P + ; R=C 4 F 9 , CPhMe F 2 , and CMeMe F 2 ) have been prepared and their reactivity with O 2 studied. The K[Cu(OR) 2 ] species react with O 2 in a copper‐concentration‐dependent manner such that 2:1 and 3:1 Cu/O 2 adducts are observed manometrically at −78 °C. Analogous reactivity with O 2 is not observed with the {K(18C6)} + or Ph 4 P + derivatives. Solution conductivity data demonstrate that these K[Cu(OR) 2 ] complexes do not behave as 1:1 electrolytes in solution. The K + ions induce aggregation of multiple [Cu(OR) 2 ] − units through K⋅⋅⋅F/O interactions and thereby effect irreversible O 2 reduction by multiple Cu centers. Bond valence analyses for the potassium cations confirm the dominance of the fluorine interactions in the coordination spheres of K + ions. Intramolecular hydroxylation of ligand aryl and alkyl CH bonds is observed. Nucleophilic reactivity with CO 2 is observed for the oxygenated Cu complexes and a Cu II carbonate has been isolated and characterized.