Solid state isomerisation reactions of some ruthenium complexes

Organometallic chemistry in the melt phase

“…Either way, the Ru complex remained in the solid state throughout the reaction. A similar result was obtained with solid 2-OMe-4-ClphenylNC, showing the generality of the reaction [65]. Reaction between RuCl 2 (PPh 3 ) 2 and liquid isonitriles also occurred without the addition of solvent at room temperature to slowly (or more rapidly at 50°C) give the required complexes in ca.…”

“…In formulating the mechanism of the isomerization reaction it was assumed that only one pair of ligands (Cl, RNC) exchanged to bring about the isomerization reaction in an intramolecular process involving no loss of ligands from the Ru during the ligand exchange. PXRD and NMR [65] techniques were used to study the reaction and results obtained were consistent with first-order kinetics with E a $ 219 (±26) kJ mol À1 indicating a high-energy process, consistent with the two ligand movement.…”

Solid-state cis–trans isomerization reaction of (η5-MeC5H4)W(CO)2P(OiPr)3I

“…This compares well with the data obtained for the 1 H NMR studies indicating that the PXRD technique can be used to monitor the kinetics of crystalline powdered materials. A similar correlation between 1 H NMR and PXRD kinetics data have been reported for the solid state isomerisation of six coordinate ruthenium complexes [17,18]. …”

trans-trans-trans-Bis(benzyl isocyanide-κC)dichlorobis(triphenylphosphine-κP)ruthenium(II) dichloromethane solvate

“…In the course of our studies of the solid-state reactions of organometallic complexes (Nareetsile et al, 2003), we have structurally characterized ttt-RuCl 2 (CNBz) 2 (PPh 3 ) 2 (t is trans, Bz is benzyl and Ph is phenyl), (I). This complex has previously been characterized in a solvent-free powdered form obtained by rapid solvent evaporation.…”

“…This complex has previously been characterized in a solvent-free powdered form obtained by rapid solvent evaporation. Solid-state isomerization of the solvent-free material from the ttt configuration to the cct form (c is cis) has been examined by differential scanning calorimetry, and IR and NMR studies (Katsuki et al, 1994;Nareetsile et al, 2003). Single crystals suitable for diffraction have been obtained, but they contain dichloromethane.…”