Solvent Dependant Ligand Displacement and Anion Coordination in Selected Copper(I) Coordination Compounds
Tóm tắt
The crystal structure of the Cu(I) mixed ligand salt, [Cu(MeCN)2(PPh3)2](CF3SO3), 1, was determined using single crystal X-ray diffraction, a = 23.249(2), b = 26.665(1), c = 19.4201(9) Å β = 102.614(1) Å, in the P21/c space group. The packing of this complex is quite similar to the PF6
−, BF4
−, and ClO4
− analogs but contains three crystallographically unique [Cu(MeCN)2(PPh3)2](CF3SO3) complexes per asymmetric unit (instead of one). Upon dissolution and recrystallization of this salt in either toluene or tetrahydrofuran, anion (and solvent) coordination results in the formation of two new neutral species Cu(PPh3)2(CF3SO3)(MeCN) 2 and Cu(PPh3)2(CF3SO3)(THF) 3, respectively. Both 2 and 3 crystallize in the orthorhombic Pca21 space group with a = 22.533(1), b = 9.0688(5), c = 18.4689(9) Å, and a = 22.434(1), b = 8.9789(5), c = 18.418(1) Å, respectively. With the perchlorate anion, [Cu2(ClO4)(MeCN)(PPh3)4(THF)](ClO4) 4, is isolated, which crystallizes in the monoclinic space group C2/c with a = 27.308(1), b = 28.064(1), c = 21.448(1) Å, and β = 120.342(1)°. Surprisingly, it is comprised of an analogous solvent coordinated neutral molecule, Cu(PPh3)2(THF)0.8(MeCN)0.2(ClO4) together with an anion-bridged dimeric species, [Cu2(PPh3)4(MeCN)1.6(THF)0.4(ClO4)]+, charge balanced by one additional non-coordinated ClO4
− anion. The coordinated solvent molecules are disordered in both moieties. Compounds 1–3 were further characterized using thermal gravimetric analysis.
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