Tri- and tetracoordinate copper(I) complexes bearing bidentate soft/hard SN and SeN ligands based on 2-aminopyridine.
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(CH(3)CN)(4)]PF(6) were studied. Treatment of CuX with EN ligands resulted in the formation of tricoordinate complexes of the type [Cu(κ(2)(E,N)-EN)X]. The reaction of [Cu(IPr)Cl] with EN ligands, followed by halide abstraction with AgSbF(6), afforded cationic tricoordinate complexes [Cu(κ(2)(S,N)-EN)(IPr)](+), while the reaction of [Cu(CH(3)CN)(4)](+) with two equivalents of EN ligands yielded tetrahedral complexes [Cu(κ(2)(E,N)-EN)(2)](+). Halide removal from [Cu(κ(2)(S,N)-SN)I] with silver salts in the presence of L = CH(3)CN and CNtBu afforded dinuclear complexes of the type [Cu(κ(2)(S,N),μ(S)-SN)(L)](2)(2+) containing bridging SN ligands. With the terminal alkynes HC≡CC(6)H(4)Me and HC≡CC(6)H(4)OMe, complexes of the formula [Cu(κ(2)(S,N)-SN-iPr)(η(2)-HC≡CC(6)H(4)Me)](+) and [Cu(κ(2)(S,N)-SN-iPr)(η(2)-HC≡CC(6)H(4)OMe)](+) were obtained. The mononuclear nature of these compounds was supported by DFT calculations. Most complexes were also characterized by X-ray crystallography.
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ABSTRACT: The title compound, C(11)H(20)N(2)PS(+)·BF(4) (-), is a salt of 2-(diisopropyl-thio-phospho-ryl-amino)-pyridine, a chelating bidentate ligand that furnishes an S atom as a soft donor and a pyridine N atom as a hard atom for transition-metal complexation. The title salt crystallizes with two formula units in the asymmetric unit. The two independent cations are protonated at the pyridine N atoms and have the S atoms syn-oriented to them so as to form bent intra-molecular N-H⋯S hydrogen bonds, one of which one is bifurcated by involving also an N-H⋯F inter-action. The phospho-ryl-amino NH groups form near linear hydrogen bonds to proximal tetra-fluoro-borate anions. Five weak C-H⋯F and three weak C-H⋯S inter-actions link the constituents into a three-dimensional framework. As a result of the crystal packing, the two cations differ notably in conformation, as can be seen from the S-P-N-C torsion angles of -18.7 (1)° in the first and -35.1 (1)° in the second cation.Acta Crystallographica Section E Structure Reports Online 06/2012; 68(Pt 6):o1835-6. · 0.35 Impact Factor