I have prepared the Ru(II) complexes having Schiff base ligands with triphenyl arsine and triphenyl phosphine under same conditions (Benzene medium, Triethylamine as a base). But Ru(II) complexes having triphenyl arsine ligands only gave cyclometallated complexes? What is the reason behind this? Please tell me.
The cyclometallation with ruthenium is usually an electrophilic substitution. Therefore triphenylarsine being a less good ligand than triphenylphosphine, the ruhenium atom having ASPh3 as a ligand is more electrophilic than with PPh3, hence the cyclometallation is easier with ruthenium complexes having the former ligand than the latter. The same is true when (benzene)RuCl2/2 is the starting material as it affords better yields of cyclometallated compound than the related (p-cymene)RuCl2/2 because p-cymene is more electron releasing than benzene, thus, the ruthenium in the second case is less electrophilic than in the first one (see Organometallics 1993,12, 4464-4472).
Article Steric control on the coordination behaviour of carbazole th...
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