Copper(I) Complexes with Thioether‐Functionalized Silylamido Ligands

Abstract The thioether‐functionalized aminosilanes Me 2 Si(NH‐C 6 H 4 ‐2‐SR) 2 (R=Ph, Me) were lithiated with n ‐BuLi and subsequently allowed to react with CuCl in the presence of PMe 3 . In the case of Me 2 Si(NH‐C 6 H 4 ‐2‐SPh) 2 , the dinuclear complex [Cu 2 {Me 2 Si(NC 6 H 4 ‐2‐SPh) 2 }(PMe 3 ) 2 ] was isolated. In [Cu 2 {Me 2 Si(NC 6 H 4 ‐2‐SPh) 2 }(PMe 3 ) 2 ] the copper atoms adopt a distorted trigonal‐planar coordination (Cu−N: 191.2(2) pm, Cu−P: 216.3(1) pm, Cu−S: 244.4(1) pm). The reaction of Li 2 Me 2 Si(N‐C 6 H 4 ‐2‐SMe) 2 with CuCl in the presence of PMe 3 led to rearrangement processes from which the ionic cluster compound [Cu(PMe 3 ) 4 ][Cu 5 {Me 2 Si(N‐C 6 H 4 ‐2‐S)(N‐C 6 H 4 ‐2‐S−Me)} 2 (PMe 3 ) 2 ] was isolated in low yield.