TY - JOUR
T1 - From AlCp*- and GaCp*-ligated ruthenium hydrides to zinc-rich heterometallic complexes
AU - Molon, Mariusz
AU - Gemel, Christian
AU - Fischer, Roland A.
PY - 2013/7
Y1 - 2013/7
N2 - The reactivity of ZnMe2 towards heteroleptic (poly)hydride ruthenium complexes was investigated. The Ru centers were coligated with different ligands including reactive low-valent ECp* (E = Ga, Al; Cp* = pentamethylcyclopentadienyl) ligands and nonreactive phosphane ligands (PCy3, PPh3, Cy = cyclohexyl, Ph = phenyl). The ECp* ligands undergo a redox reaction together with Cp*/Me group exchange when treated with ZnMe2 to form two equivalents of ZnR (R = Cp*, Me) units, and ER3 species are liberated. Similarly, Ru-H moieties react with ZnMe2 to form one equivalent of ZnMe and one equivalent of CH4. The 18-electron rule proved valid for the rationalization of the obtained compositions; one ECp* or phosphane ligand is equivalent to two one-electron ZnR or H ligands. The factors that control the exchange of phosphane or hydride ligands are discussed. All compounds were characterized by NMR and IR spectroscopy, liquid injection field desorption ionization (LIFDI) MS analysis, single-crystal X-ray diffraction, and elemental analysis. Three heteroleptic ruthenium hydride complexes [Ru(PCy 3)(ZnCp*)2(ZnMe)6] (Cp* = pentamethylcyclopentadienyl), [Ru(PPh3)2(ZnCp*) 2(ZnMe)2(H)2], and [Ru(PCy3) 2(ZnMe)2(μ2-H)4] have been synthesized and characterized by NMR and IR spectroscopy, MS analysis, single-crystal X-ray diffraction, and elemental analysis. The influence of the phosphane ligand on the product formed is discussed.
AB - The reactivity of ZnMe2 towards heteroleptic (poly)hydride ruthenium complexes was investigated. The Ru centers were coligated with different ligands including reactive low-valent ECp* (E = Ga, Al; Cp* = pentamethylcyclopentadienyl) ligands and nonreactive phosphane ligands (PCy3, PPh3, Cy = cyclohexyl, Ph = phenyl). The ECp* ligands undergo a redox reaction together with Cp*/Me group exchange when treated with ZnMe2 to form two equivalents of ZnR (R = Cp*, Me) units, and ER3 species are liberated. Similarly, Ru-H moieties react with ZnMe2 to form one equivalent of ZnMe and one equivalent of CH4. The 18-electron rule proved valid for the rationalization of the obtained compositions; one ECp* or phosphane ligand is equivalent to two one-electron ZnR or H ligands. The factors that control the exchange of phosphane or hydride ligands are discussed. All compounds were characterized by NMR and IR spectroscopy, liquid injection field desorption ionization (LIFDI) MS analysis, single-crystal X-ray diffraction, and elemental analysis. Three heteroleptic ruthenium hydride complexes [Ru(PCy 3)(ZnCp*)2(ZnMe)6] (Cp* = pentamethylcyclopentadienyl), [Ru(PPh3)2(ZnCp*) 2(ZnMe)2(H)2], and [Ru(PCy3) 2(ZnMe)2(μ2-H)4] have been synthesized and characterized by NMR and IR spectroscopy, MS analysis, single-crystal X-ray diffraction, and elemental analysis. The influence of the phosphane ligand on the product formed is discussed.
KW - Cluster compounds
KW - Coordination compounds
KW - Hydrides
KW - Ruthenium
KW - Zinc
UR - http://www.scopus.com/inward/record.url?scp=84880179818&partnerID=8YFLogxK
U2 - 10.1002/ejic.201300317
DO - 10.1002/ejic.201300317
M3 - Article
AN - SCOPUS:84880179818
SN - 1434-1948
SP - 3616
EP - 3622
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 21
ER -