Flexibility and lability of a phenyl ligand in hetero-organometallic 3d metal–Sn(iv) compounds and their catalytic activity in Baeyer–Villiger oxidation of cyclohexanone

Abstract

The single compartmental Schiff base N,N′-ethylenebis(salicylaldimine) (H₂L) and [SnPh₂Cl₂] were utilized to synthesize heterobimetallic 3d metal–Sn complexes, the Co^IIISn^IV compound [{SnPhCl₂}(1κO²N²,2κO²-μ-L)(μ-OMe){CoPh}] (1), the Ni^IISn^IV compound [{SnPh₂Cl₂}(1κO²N²,2κO²-μ-L)Ni] (2) and the Cu^IISn^IV compound [{SnPh₂Cl₂}(1κO²N²,2κO²-μ-L)Cu] (3). Attempting to prepare the ethoxido bridged compound analogous to 1 (in ethanol) gives the phenylcobalt(III) complex [Co(κO²N²)Ph(H₂O)] (1A). Single crystal X-ray structure analyses reveal that 1 is derived from an intermetallic (Sn to Co) phenyl shift and that 1A is a transmetallated product; in compounds 2 and 3, the phenyl groups remain coordinated to Sn^IV but one of the π rings interacts with the 3d-metal. Thus, while systems 1 and 1A show the lability of the phenyl ligand, 2 and 3 reveal its flexible nature. Theoretical DFT calculations demonstrate that the conceivable Ph group shift occurs in the oxidized Co^III intermediate [{Sn^IVPh₂Cl₂}(κO₂N₂-μ-L){Co^III(MeO)}] (5) rather than in the corresponding Co^II species [{Sn^IVPh₂Cl₂}(κO₂N₂-μ-L){Co^II(MeOH)}] (4). Their catalytic studies in the Baeyer–Villiger oxidation of cyclohexanone into ε-caprolactone with two different oxidants reveal that the sacrificial aldehyde method (with dioxygen/benzaldehyde) is better than that with aqueous H₂O₂ (30%). The effects of various reaction parameters such as solvent, catalyst amount, temperature, time and heating method were studied allowing the achievement of yields up to 83% with 89% selectivity.