title: A Mixed-Valence Tri-Zinc Complex, [LZnZnZnL] (L=Bulky Amide), Bearing a Linear Chain of Two-Coordinate Zinc Atoms.
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}2Pr(i)-2,6,4); and the formally zinc(0) complex, [L*ZnMg((Mes)Nacnac)] (L*=N(Ar*)(SiPr(i)3); Ar*=C6H2{C(H)Ph2}2Me-2,6,4; (Mes)Nacnac=[(MesNCMe)2CH](-), Mes=mesityl), which contains the first unsupported Zn-Mg bond. Two equivalents of [L*ZnMg((Mes)Nacnac)] react with ZnBr2 or ZnBr2(tmeda) to give the mixed valence, two-coordinate, linear tri-zinc complex, [L*Zn(I)Zn(0)Zn(I)L*], 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.
authors.affiliation: School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia) http://monash.edu/science/jonesgroup.
authors.forename: Jamie
authors.initials: J
authors.lastname: Hicks
authors.affiliation: School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia) http://monash.edu/science/jonesgroup.
authors.forename: Emma J
authors.initials: EJ
authors.lastname: Underhill
authors.affiliation: Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, 31077 Toulouse (France).
authors.forename: Christos E
authors.initials: CE
authors.lastname: Kefalidis
authors.affiliation: Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, 31077 Toulouse (France). laurent.maron@irsamc.ups-tlse.fr.
authors.forename: Laurent
authors.initials: L
authors.lastname: Maron
authors.affiliation: School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia) http://monash.edu/science/jonesgroup. cameron.jones@monash.edu.
authors.forename: Cameron
authors.initials: C
authors.lastname: Jones
keywords: DFT calculations; magnesium; metal-metal bonding; mixed valence; zinc