TY - JOUR
T1 - A Mixed-Valence Tri-Zinc Complex, [LZnZnZnL] (L = Bulky Amide), Bearing a Linear Chain of Two-Coordinate Zinc Atoms
AU - Hicks, Jamie
AU - Underhill, Emma J.
AU - Kefalidis, Christos E.
AU - Maron, Laurent
AU - Jones, Cameron
PY - 2015/8/17
Y1 - 2015/8/17
N2 - 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 dagger)(SiMe3), Ar dagger= C6H2{C(H)Ph-2}(2)Pr-i-2,6,4); and the formally zinc(0) complex, [L*ZnMg((Mes)Nacnac)] (L*= N(Ar*)(SiPr3i); Ar*= C6H2{C(H)Ph-2}(2)Me-2,6,4; (Mes)Nacnac=[(MesNCMe)(2)CH](-), 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*(ZnZnZnL)-Zn-I-Zn-0-L-I*], 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.
AB - 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 dagger)(SiMe3), Ar dagger= C6H2{C(H)Ph-2}(2)Pr-i-2,6,4); and the formally zinc(0) complex, [L*ZnMg((Mes)Nacnac)] (L*= N(Ar*)(SiPr3i); Ar*= C6H2{C(H)Ph-2}(2)Me-2,6,4; (Mes)Nacnac=[(MesNCMe)(2)CH](-), 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*(ZnZnZnL)-Zn-I-Zn-0-L-I*], 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.
KW - DFT calculations
KW - Magnesium
KW - Metal-metal bonding
KW - Mixed valence
KW - Zinc
UR - https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=anu_research_portal_plus2&SrcAuth=WosAPI&KeyUT=WOS:000360215100046&DestLinkType=FullRecord&DestApp=WOS_CPL
U2 - 10.1002/anie.201504818
DO - 10.1002/anie.201504818
M3 - Article
C2 - 26126428
SN - 1433-7851
VL - 54
SP - 10000
EP - 10004
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 34
ER -