First Copper(I) and Silver(I) Complexes Containing Phosphanylphosphido Ligands

Three new complexes with phosphanylphosphido ligands, [Cu 4 { μ 2 ‐P(SiMe 3 )‐P t Bu} 4 ] ( 1 ), [Ag 4 { μ 2 ‐P(SiMe 3 )‐P t Bu 2 } 4 ] ( 2 ) and [Cu{ η 1 ‐P(SiMe 3 )‐P i Pr 2 } 2 ] – [Li(Diglyme) 2 ] + ( 3 ) were synthesized and structurally characterized by X‐ray diffraction, NMR spectroscopy, and elemental analysis. Complexes 1 and 2 were obtained in the reactions of lithium derivative of diphosphane t Bu 2 P‐P(SiMe 3 )Li · 2.7THF with CuCl and [ i Bu 3 PAgCl] 4 , respectively. The X‐ray diffraction analysis revealed that the complexes 1 and 2 present macrocyclic, tetrameric form with Cu 4 P 4 and Ag 4 P 4 core. Complex 3 was prepared in the reaction of CuCl with a different derivative of lithiated diphosphane i Pr 2 P‐P(SiMe 3 )Li · 2(Diglyme). Surprisingly, the X‐ray analysis of 3 revealed that in this reaction instead of the tetramer the monomeric form, ionic complex [Cu{ η 1 ‐P(SiMe 3 )‐P i Pr 2 } 2 ] – [Li(Diglyme) 2 ] + was formed.