Reactivity of Cu(I) Compounds towards Ethylenediamine and Dimethylformamide: Crystal Structure of CuCl(PiPr3)n (n=1, 2), CuX(PPh3)(en)2 (X=Cl, Br) and CuX(PPh3)(dmf)
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32
摘要:
The synthesis of several phosphine Cu(I) complexes is reported, and their reactivity towards the solvents ethylenediamine (en) and dimethylformamide (dmf) has been investigated. CuX(PPh<sub>3</sub>) [X = Cl , Br (2)], CuCl(PCy<sub>3</sub>) (3) and CuCl(P<sup>i</sup>Pr<sub>3</sub>)<sub>n</sub> [n = 1 (4), 2 (5)] were prepared according to adapted literature procedures. The complexes CuCl(P<sup>i</sup>Pr<sub>3</sub>)n were obtained in crystalline form from a hexane solution at -70 °C and structurally characterized for n = 1 and 2. Copper halide complexes of PCy<sub>3</sub> (3) and P<sup>i</sup>Pr<sub>3</sub> [n=1 (4)] gave colorless solutions in both en and dmf indicating the absence of Cu(II) ions. CuCl(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> is stable in dmf solutions. By contrast, the complexes CuX(PPh<sub>3</sub>) (X = Cl, Br) dissolve with blue color in en and with greenish-yellow color in dmf at higher temperatures under inert gas indicating a redox process affording Cu(II). At room temperature colorless crystals of CuX(PPh<sub>3</sub>)(en)<sub>2</sub> [X = Cl (6), Br (7)] and CuX(PPh<sub>3</sub>)(dmf) [X = Cl (8), Br (9)] were isolated from the solutions and analyzed by single-crystal X-ray diffraction.
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DOI:
10.5560/znb.2012-0101
年份:
2012
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