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)

Abstract

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 3 ) [X = Cl (1), Br (2)], CuCl(PCy 3 ) (3) and CuCl(P i Pr 3 ) n [n = 1 (4), 2 (5)] were prepared according to adapted literature procedures. The complexes CuCl(P i Pr 3 ) 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 3 (3) and P i Pr 3 [n = 1 (4)] gave colorless solutions in both en and dmf indicating the absence of Cu(II) ions. CuCl(P i Pr 3 ) 2 is stable in dmf solutions. By contrast, the complexes CuX(PPh 3 ) (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 3 )(en) 2 [X = Cl (6), Br (7)] and CuX(PPh 3 )(dmf) [X = Cl (8), Br (9)] were isolated from the solutions and analyzed by single-crystal X-ray diffraction.

On the Reactivity of Silylated Ge9 Clusters: Synthesis and Characterization of [ZnCp*(Ge9{Si(SiMe3)3}3)], [CuPiPr3(Ge9{Si(SiMe3)3}3)], and [(CuPiPr3)4{Ge9(SiPh3)2}2]

“…The solvents ACN, hexane, Et 2 O, and toluene were dried over molecular sieves (3 Å, 4 Å) and THF over a special drying material in a solvent purificator (MBraun MB‐SPS). [ZnCp* 2 ] and [CuP i Pr 3 Cl] were synthesized according to the literature. All other chemicals were received commercially and used without further purification.…”