A Mixed‐Valence Tri‐Zinc Complex, [LZnZnZnL] (L=Bulky Amide), Bearing a Linear Chain of Two‐Coordinate Zinc Atoms |
| |
| Authors: | Jamie Hicks Emma J Underhill Dr Christos E Kefalidis Prof Laurent Maron Prof Cameron Jones |
| |
| Institution: | 1. School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia) http://monash.edu/science/jonesgroup;2. Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, 31077 Toulouse (France) |
| |
| Abstract: | Reduction of a variety of extremely bulky amido Group 12 metal halide complexes, LMX(THF)0,1] (L=amide; M=Zn, Cd, or Hg; X=halide) with a magnesium(I) dimer gave a homologous series of two‐coordinate metal(I) dimers, L′MML′] (L′=N(Ar?)(SiMe3), Ar?=C6H2{C(H)Ph2}2Pri‐2,6,4); and the formally zinc(0) complex, L*ZnMg(MesNacnac)] (L*=N(Ar*)(SiPri3); Ar*=C6H2{C(H)Ph2}2Me‐2,6,4; MesNacnac=(MesNCMe)2CH]?, Mes=mesityl), which contains the first unsupported Zn? Mg bond. Two equivalents of L*ZnMg(MesNacnac)] react with ZnBr2 or ZnBr2(tmeda) to give the mixed valence, two‐coordinate, linear tri‐zinc complex, L*ZnIZn0ZnIL*], and the first zinc(I) halide complex, L*ZnZnBr(tmeda)], respectively. The analogues L*ZnMZnL*] (M=Cd or Hg), were also prepared, the Cd species contains the first Zn? Cd bond in a molecular compound. Metal–metal bonding was studied by DFT calculations. |
| |
| Keywords: | DFT calculations magnesium metal– metal bonding mixed valence zinc |
|
|
