Solution behavior and structural properties of Cu(I) complexes featuring m-terphenyl isocyanides |
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Authors: | Fox Brian J Sun Queena Y DiPasquale Antonio G Fox Alexander R Rheingold Arnold L Figueroa Joshua S |
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Institution: | Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, California 92093-0358, USA. |
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Abstract: | The synthesis of the m-terphenyl isocyanide ligand CNAr (Mes2) (Mes = 2,4,6-Me 3C 6H 2) is described. Isocyanide CNAr (Mes2) readily functions as a sterically encumbering supporting unit for several Cu(I) halide and pseudo halide fragments, fostering in some cases rare structural motifs. Combination of equimolar quantities of CNAr (Mes2) and CuX (X = Cl, Br and I) in tetrahydrofuran (THF) solution results in the formation of the bridging halide complexes (mu-X) 2Cu(THF)(CNAr (Mes2))] 2. Addition of CNAr (Mes2) to cuprous chloride in a 2:1 molar ratio generates the complex ClCu(CNAr (Mes2)) 2 in a straightforward manner. Single-crystal X-ray diffraction has revealed ClCu(CNAr (Mes2)) 2 to exist as a three-coordinate monomer in the solid state. As determined by solution (1)H NMR and FTIR spectroscopic studies, monomer ClCu(CNAr (Mes2)) 2 resists tight binding of a third CNAr (Mes2) unit, resulting in rapid isocyanide exchange. Contrastingly, addition of 3 equiv of CNAr (Mes2) to cuprous iodide readily affords the tris-isocyanide species, ICu(CNAr (Mes2)) 3, as determined by X-ray diffraction. Similar coordination behavior is observed in the tris-isocyanide salt (THF)Cu(CNAr (Mes2)) 3]OTf (OTf = O 3SCF 3), which is generated upon treatment of (C 6H 6)Cu(OTf)] 2 with 6 equiv of CNAr (Mes2) in THF. The disparate coordination behavior of the CuCl] fragment relative to both CuI] and CuOTf] is rationalized in terms of structure and Lewis acidity of the Cu-containing fragments. The putative triflate species Cu(CNAr (Mes2)) 3]OTf itself serves as a good Lewis acid and is found to weakly bind C 6H 6 in an eta (1)- C manner in the solid-state. Density Functional Theory is used to describe the bonding and energetics of the eta (1)- C Cu-C 6H 6 interaction. |
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