A Mixed‐Valence Tri‐Zinc Complex, [LZnZnZnL] (L=Bulky Amide), Bearing a Linear Chain of Two‐Coordinate Zinc Atoms1. (30th June 2015)

• Record Type: Journal Article
• Authors: Hicks, Jamie; Underhill, Emma J.; Kefalidis, Christos E.; Maron, Laurent; Jones, Cameron
• Is Part Of: Angewandte Chemie. Volume 127:Number 34(2015)
• Page Start: 10138
• Page End: 10142
• Publication Date: 2015-06-30
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201504818
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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*Zn^IZn⁰Zn^IL*], 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.</p> </abstract>