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Preparation of Diamine‐β‐diketiminato Copper(II) Complexes and Their Application in the Reverse Atom‐Transfer Radical Polymerization of Styrene
Author(s) -
Champouret Yohan,
Gulli Stefano,
Daran JeanClaude,
Poli Rinaldo
Publication year - 2012
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.201200008
Subject(s) - disproportionation , chemistry , styrene , polymerization , polymer chemistry , catalysis , toluene , copper , diamine , atom transfer radical polymerization , yield (engineering) , radical polymerization , medicinal chemistry , photochemistry , copolymer , organic chemistry , polymer , materials science , metallurgy
Compound Et 2 NCH 2 CH 2 N=C(Me)CH=C(Me)NHCH 2 CH 2 NEt 2 (HL), after conversion to the Li + salt with use of MeLi, reacts with CuCl 2 in toluene to yield CuClL ( 1 ). The compound adopts a four‐coordinate CuClN 3 environment with a pendant amino arm. The same reaction with CuCl and[Cu(MeCN) 4 ]BF 4 leads to disproportionation with deposition of metallic copper. Crystals of compounds [CuL][CuCl 2 ] ( 2 ) and [CuL]BF 4 ( 3 ) were isolated in minor amounts from these reactions. The [CuL] + ion in these compounds has a four‐coordinate CuN 4 environment. Compound 2 was also obtained in good yields from the reaction between equivalent amounts of 1 and CuCl. Compound 1 was used to control the radical polymerization of styrene under ARGET ATRP conditions in the presence of glucose as reducing agent and bromoethylbenzene as initiator. The polymerization behavior indicates that the controlling ability of this system is negatively affected by its slow trapping rate and by the disproportionation of the CuL catalyst.