Linking of CuI Units by Tetrahedral Mo2 E2 Complexes (E=P, As).

The reaction of [Cp2 Mo2 (CO)4 (μ,η2:2 -E2 )] (A: E=P, B: E=As, Cp=C5 H5 ) with the WCA-containing CuI salts ([Cu(CH3 CN)4 ][Al{OC(CF3 )3 }4 ] (CuTEF, C), [Cu(CH3 CN)4 ][BF4 ] (D) and [Cu(CH3 CN)3.5 ][FAl{OC6 F10 (C6 F5 )}3 ] (CuFAl, E)) affords seven unprecedented coordination compounds. Depending on the E2 ligand complex, the counter anion of the copper salt and the stoichiometry, four dinuclear copper dimers and three trinuclear copper compounds are accessible. The latter complexes reveal first linear Cu3 arrays linked by E2 units (E=P, As) coordinated in an η2:1:1 coordination mode. All compounds were characterized by X-ray crystallography, NMR and IR spectroscopy, mass spectrometry and elemental analysis. To define the nature of the Cu⋅⋅⋅Cu⋅⋅⋅Cu interactions, DFT calculations were performed.