title: Reactivity of TCNE and TCNQ derivatives of quinonoid zwitterions with Cu(I).
abstract: The reactions of TCNE- and TCNQ-functionalized (TCNE: tetracyanoethylene and TCNQ: 7,7',8,8'-tetracyanoquinodimethane) zwitterionic benzoquinonemonoimines with a Cu(I)-BIAN complex (BIAN = bis(o,o'-bisisopropylphenyl)acenaphthenequinonediimine) have been investigated and found to follow a diversity of interesting patterns. The complexes [Cu(BIAN)(NCMe)(L2)]BF4 (2) and [Cu(BIAN)(L2)2]BF4 (4) were obtained by reacting [Cu(BIAN)(NCMe)2]BF4 (1) with one and two equivalents of L2, respectively. Following similar procedures, the complexes [Cu(BIAN)(NCMe)(L3)]BF4 (6) and [Cu(BIAN)(L3)2]BF4 (7) were obtained by reaction of 1 with L3. The reaction of 2 with 0.5 equiv. of 4,4'-bipyridine afforded [{Cu(BIAN)(L2)}2(μ-4,4'-bipyridine)](BF4)2 (3). The complexes were characterized by multinuclear NMR, IR and UV-Vis spectroscopic techniques, mass spectrometry, cyclic voltammetry and elemental analysis. The molecular structures of complexes 3 ·4CH2Cl2 and 4 ·CH2Cl2 were determined by single crystal X-ray diffraction. An unexpected coordination polymer [Cu((L2-))2]∞ (5) was also structurally characterized, which contains Cu(II) centres chelated by two N,O-bound ligands resulting from the monodeprotonation of L2.
authors.affiliation: Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, F-67081 Strasbourg Cedex, France. braunstein@unistra.fr.
authors.forename: Thomas
authors.initials: T
authors.lastname: Kauf
authors.forename: Vitor
authors.initials: V
authors.lastname: Rosa
authors.forename: Christophe
authors.initials: C
authors.lastname: Fliedel
authors.forename: Roberto
authors.initials: R
authors.lastname: Pattacini
authors.forename: Naina
authors.initials: N
authors.lastname: Deibel
authors.forename: Teresa
authors.initials: T
authors.lastname: Avilés
authors.forename: Biprajit
authors.initials: B
authors.lastname: Sarkar
authors.forename: Pierre
authors.initials: P
authors.lastname: Braunstein