Tri- and tetracoordinate copper(i) complexes bearing bidentate soft/hard SN and SeN ligands based on 2-aminopyridine?

Dalton Transactions Pub Date: 2011-06-07 DOI: 10.1039/C1DT10377F

Abstract

The coordination properties of the EN ligands N-(2-pyridinyl)amino-diphenylphosphine sulfide, N-(2-pyridinyl)amino-diisopropylphosphine sulfide, N-(2-pyridinyl)amino-diphenylphosphine selenide, N-(2-pyridinyl)amino-diisopropylphosphine selenide towards copper(I) precursors CuX (X = Br, I), [Cu(IPr)Cl] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), and [Cu(CH3CN)4]PF6 were studied. Treatment of CuX with EN ligands resulted in the formation of tricoordinate complexes of the type [Cu(κ2(E,N)-EN)X]. The reaction of [Cu(IPr)Cl] with EN ligands, followed by halide abstraction with AgSbF6, afforded cationic tricoordinate complexes [Cu(κ2(S,N)-EN)(IPr)]+, while the reaction of [Cu(CH3CN)4]+ with two equivalents of EN ligands yielded tetrahedral complexes [Cu(κ2(E,N)-EN)2]+. Halide removal from [Cu(κ2(S,N)-SN)I] with silver salts in the presence of L = CH3CN and CNtBu afforded dinuclear complexes of the type [Cu(κ2(S,N),μ(S)-SN)(L)]22+ containing bridging SN ligands. With the terminal alkynes HC[triple bond, length as m-dash]CC6H4Me and HC[triple bond, length as m-dash]CC6H4OMe, complexes of the formula [Cu(κ2(S,N)-SN-iPr)(η2-HC[triple bond, length as m-dash]CC6H4Me)]+ and [Cu(κ2(S,N)-SN-iPr)(η2-HC[triple bond, length as m-dash]CC6H4OMe)]+ were obtained. The mononuclear nature of these compounds was supported by DFT calculations. Most complexes were also characterized by X-ray crystallography.

Graphical abstract: Tri- and tetracoordinate copper(i) complexes bearing bidentate soft/hard SN and SeN ligands based on 2-aminopyridine
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