TY - JOUR
T1 - Synthesis and Characterisation of Diruthenium Paddlewheel Compounds Bearing 2,6-Di(p-tolyl)benzoate Ligands
AU - Gracia, Raquel
AU - Patmore, Nathan J.
PY - 2010/9/1
Y1 - 2010/9/1
N2 - The mixed carboxylate diruthenium complexes trans-[Ru2II,III(O2CCH3)2(O2CAr)2Cl] (I) and trans-[Ru2II,II(O2CCH3)2(O2CAr)2] (II) (O2CAr = 2,6-di(p-tolyl)benzoate) have been synthesised along with [Ru2II,III(O2CAr)4Cl] (III) and the homoleptic complex [Ru2II,II(O2CAr)4] (IV). The structures trans-[Ru2(O2CCH3)2(O2CAr)2Cl(thf)]·(thf) and [Ru2(O2CAr)4Cl(η1-CH2Cl2)] were determined by X-ray crystallography, and display the expected paddlewheel arrangement of the carboxylate ligands around the diruthenium core. The structure of III is a rare example of a structurally characterised dichloromethane complex, highlighting the Lewis acidic nature of the diruthenium axial position. The bulky -O2CAr ligand protects the axial positions from intermolecular interactions in the absence of strong nucleophiles for III and IV, and the effect this has on the electronic structure of the diruthenium core in these complexes was investigated by cyclic voltammetry, electronic absorption spectroscopy and magnetic susceptibility studies.
AB - The mixed carboxylate diruthenium complexes trans-[Ru2II,III(O2CCH3)2(O2CAr)2Cl] (I) and trans-[Ru2II,II(O2CCH3)2(O2CAr)2] (II) (O2CAr = 2,6-di(p-tolyl)benzoate) have been synthesised along with [Ru2II,III(O2CAr)4Cl] (III) and the homoleptic complex [Ru2II,II(O2CAr)4] (IV). The structures trans-[Ru2(O2CCH3)2(O2CAr)2Cl(thf)]·(thf) and [Ru2(O2CAr)4Cl(η1-CH2Cl2)] were determined by X-ray crystallography, and display the expected paddlewheel arrangement of the carboxylate ligands around the diruthenium core. The structure of III is a rare example of a structurally characterised dichloromethane complex, highlighting the Lewis acidic nature of the diruthenium axial position. The bulky -O2CAr ligand protects the axial positions from intermolecular interactions in the absence of strong nucleophiles for III and IV, and the effect this has on the electronic structure of the diruthenium core in these complexes was investigated by cyclic voltammetry, electronic absorption spectroscopy and magnetic susceptibility studies.
KW - Carboxylate ligands
KW - Metal-metal interactions
KW - Ruthenium
UR - http://www.scopus.com/inward/record.url?scp=77956427106&partnerID=8YFLogxK
U2 - 10.1007/s10876-010-0310-1
DO - 10.1007/s10876-010-0310-1
M3 - Article
AN - SCOPUS:77956427106
VL - 21
SP - 339
EP - 350
JO - Journal of Cluster Science
JF - Journal of Cluster Science
SN - 1040-7278
IS - 3
ER -