Controlled Copper-Mediated Chlorination of Phenol Rings under Mild
Conditions
Yu-Fei Song
Gerard A. van Albada
Jinkui Tang
Ilpo Mutikainen
Urho Turpeinen
Chiara Massera
Olivier Roubeau
José Sanchez Costa
Patrick Gamez
Jan Reedijk
10.1021/ic070057n.s007
https://acs.figshare.com/articles/dataset/Controlled_Copper_Mediated_Chlorination_of_Phenol_Rings_under_Mild_Conditions/3002566
The very unusual case of copper-mediated chlorination of phenol rings under mild conditions at room temperature
is reported. Reaction of the ligand 1,7-bis(2-hydroxyphenyl)-2,6-diaza-4-hydroxylheptane (H<sub>3</sub>L1) with CuCl<sub>2</sub> in
acetonitrile leads to either the formation of a tetranuclear copper(II) complex [Cu<sub>4</sub>(HL3)<sub>2</sub>(μ-Cl)<sub>2</sub>Cl<sub>2</sub>](CH<sub>3</sub>CN) (<b>1</b>) or
a linear trinuclear complex [Cu<sub>3</sub>(HL1)<sub>2</sub>Cl<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub>](CH<sub>3</sub>CN)<sub>2</sub> (<b>2</b>), depending on the reaction conditions. Both
compounds have been fully characterized, including the determination of their 3D structures by X-ray diffraction.
The unprecedented tetranuclear compound <b>1</b> is constituted of a dichlorido-bridged dimer of di-μ-phenoxido-dinuclear
species, whereas the trinuclear complex <b>2</b> presents a linear array of copper(II) ions, held together through di-μ-phenoxido bridges of the central and external ions. The magnetic susceptibility of the two compounds was investigated,
revealing either very strong (<i>J</i> < −500 cm<sup>-1</sup>) or strong (<i>J</i> value around −370(1) cm<sup>-1</sup>) antiferromagnetic dominant
interactions among the Cu<sup>II</sup> ions for <b>1</b> and <b>2</b>, respectively. The tetranuclear complex <b>1</b> is obtained, under dry
conditions, through the in situ formation of ligand HL3 (H<sub>3</sub>L3 = 1,7-bis(2-hydroxy-5-chlorophenyl)-2,6-diaza-4-hydroxylheptane) by oxidative chlorination of (HL1)<sup>2-</sup>. In the presence of traces of water, <b>1</b> is partially hydroxylated
at the ortho position of one of the phenyl rings. The use of trimethylorthoformate as the dehydrating agent prevents
the formation of hydroxylated ligands. Several partly chlorinated/hydroxylated products (identified as H<sub>3</sub>L2) have
also been obtained through slight variations of the synthetic procedures (presence or absence of water and/or
triethylamine in the reaction mixtures). These partially chlorinated and/or hydroxylated coordination species are
mutually isomorphous to either <b>1</b> or <b>2</b>. Several “modified” ligands have been isolated and characterized by <sup>1</sup>H NMR
and MS, after reaction with sodium sulfide of the complexes formed.
2007-06-11 00:00:00
3 D structures
trinuclear
phenyl rings
ligand HL 3
tetranuclear compound 1
sodium sulfide
Cu II ions
H 3 L 3
1 H NMR
Cu 3
Cu 4
bi
formation
MS
CuCl 2
cm
presence
CH 3 CN
Phenol Rings
J value
dehydrating agent
reaction mixtures
reaction conditions
chlorinated
Several
species
ortho position
Mild Conditions
phenol rings
hydroxylated ligands
oxidative chlorination
room temperature