Influence of Second Coordination Sphere Hydroxyl Groups on the Reactivity of Copper(I) Complexes
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https://figshare.com/articles/dataset/Influence_of_Second_Coordination_Sphere_Hydroxyl_Groups_on_the_Reactivity_of_Copper_I_Complexes/2530801
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资源简介：
We report the enhanced reactivity of hydroxyl substituted
CuN3+ derivatives, where N3 = tris(picolinyl)methane
(tripic) and related derivatives, upon deprotonation of the O–H
functionality. The work capitalizes on new methodology for incorporating
hydroxyl groups into the second coordination sphere of copper centers.
The key synthetic methodology relies on Pd-catalyzed coupling reactions
of dilithiated 6-methyl-2-pyridone with bromopyridyl derivatives.
These building blocks allow the preparation of tridentate N3 ligands with OH and OMe substituents flanking the fourth coordination
site of a tetrahedral complex. Coupling of these tridendate ligands
gives the corresponding hydroxy- and methoxy-functionalized bistripodal
ligands. [Cu[bis(2-methylpyrid-6-yl)(2-hydroxypyrid-6-yl)methane](NCMe)]+ ([Cu(2H)(NCMe)]+) oxidizes readily
in air to afford the mixed valence Cu1.5 dimer ([Cu2(2)2]+). Formation of [Cu2(2)2]+ is accelerated in
the presence of base and can be reversed with a combination of decamethylferrocene
and acid. The reactivity of [Cu(2H)(NCMe)]+ with dioxygen requires deprotonation of the hydroxyl substituent:
neither [Cu(tripic)(NCMe)]+ nor the methoxy-derivatives
displayed comparable reactivity. A related mixed valence dimer formed
upon oxidation of the dicopper(I) complex of a tetrahydroxy
bis(tridentate) ligand, [Cu2(6H4)(NCMe)2]2+. The dicopper(I) complex
of the analogous tetramethoxy N6-ligand, [Cu2(5)(NCMe)2]2+, instead reversibly
binds O2. Deprotonation of [Cu(2H)(CO)]+ and [Cu(2H)(NCMe)]+ afforded the
neutral derivatives Cu(2)(CO) and Cu2(2)2, respectively. The dicopper(I)
derivative Cu2(2)2 can be reoxidized,
reprotonated, and carbonylated. The silver(I) complex,
[Ag(2H)(NCMe)]BF4, forms an analogous neutral
dimer (Ag2(2)2) upon deprotonation
of the hydroxyl group. The structures of ligand 2H, [Cu2(5)(NCMe)2]+, [Cu2(2)2]+, [Cu2(6H2)]+, [Ag(2H)(NCMe)]BF4, and Ag2(2)2 were confirmed
by single crystal X-ray diffraction.
创建时间：
2016-02-21
