TY - JOUR
T1 - Organometallic chemistry of Ga+
T2 - Formation of an unusual gallium dimer in the coordination sphere of ruthenium
AU - Cadenbach, Thomas
AU - Gemel, Christian
AU - Bollermann, Timo
AU - Fernandez, Israel
AU - Frenking, Gernot
AU - Fischer, Roland A.
PY - 2008/11/26
Y1 - 2008/11/26
N2 - New insights into the distinct organometallic chemistry of the Ga + ion are presented. Ga+ reacts as a strong electrophile with the electron rich ligand trismethylene-methane (C(CH2) 32-) attached at Ru by insertion into a Ru-C bond. The resulting "gallamethylallyl" ligand behaves like strong nucleophile similar to known monovalent GaR species. This donor property leads to the dimeric structure of the product [ (Ru(GaCp*)3- [η3-(CH2)2C{CH2(μ-Ga)}]} 2][(BArF)2] (4) (Cp* = C 5Me5, [BArF] = [B{C6H 3-(CF3)2}4]). Very unexpectedly, the two gallium ligands in this dimer are found in close vicinity to each other with a distance in the range of Ga-Ga bonds. Indeed, AIM calculations confirm a weak attractive closed shell Ga-Ga interaction. Finally, a novel example of a complex with substituent-free Ga+ as a ligand was found in the compound [Ru(PCy3)2(GaCp*)2(Ga)][BAr F] (6) (Cy = C6H11, cyclohexyl), the very short Ru-Ga bond length confirming the assumption that Ga+ represents a pure σ/π-accepting ligand in this case.
AB - New insights into the distinct organometallic chemistry of the Ga + ion are presented. Ga+ reacts as a strong electrophile with the electron rich ligand trismethylene-methane (C(CH2) 32-) attached at Ru by insertion into a Ru-C bond. The resulting "gallamethylallyl" ligand behaves like strong nucleophile similar to known monovalent GaR species. This donor property leads to the dimeric structure of the product [ (Ru(GaCp*)3- [η3-(CH2)2C{CH2(μ-Ga)}]} 2][(BArF)2] (4) (Cp* = C 5Me5, [BArF] = [B{C6H 3-(CF3)2}4]). Very unexpectedly, the two gallium ligands in this dimer are found in close vicinity to each other with a distance in the range of Ga-Ga bonds. Indeed, AIM calculations confirm a weak attractive closed shell Ga-Ga interaction. Finally, a novel example of a complex with substituent-free Ga+ as a ligand was found in the compound [Ru(PCy3)2(GaCp*)2(Ga)][BAr F] (6) (Cy = C6H11, cyclohexyl), the very short Ru-Ga bond length confirming the assumption that Ga+ represents a pure σ/π-accepting ligand in this case.
KW - Density functional calculations
KW - Gallium
KW - Low-valent ion
KW - Metal-metal interactions
KW - Ruthenium
UR - http://www.scopus.com/inward/record.url?scp=56749091493&partnerID=8YFLogxK
U2 - 10.1002/chem.200801328
DO - 10.1002/chem.200801328
M3 - 文章
AN - SCOPUS:56749091493
SN - 0947-6539
VL - 14
SP - 10789
EP - 10796
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 34
ER -