One-pot synthesis of cobalt complexes with 2,6-bis(arylimino)phenoxyl/phenthioxyl ligands and catalysis on isoprene...

Several cobalt complexes supported by 2,6-bis(arylimino)phenoxyl/phenthioxyl ligands κ2N,X-Ar[NXN]CoCl(THF) (1a, X = O, Ar = 2,6-Me2C6H3; 1b, X = O, Ar = 2,6-iPr2C6H3; 2a, X = S, Ar = 2,6-Me2C6H3; 2b, X = S, Ar = 2,6-iPr2C6H3) were synthesized by direct oxygen(sulfur) insertion into the C-Co bond of the mixed-valence cobalt complexes {κ2C,N,η6-Ar[NCN]Co-κN-CoCl(μ-Cl)}2. Crystallization of 1b in the presence of water gave the hydrolysis product 1b'. Treatment of Ar[NCN]Li with dioxygen followed by the addition of CoCl2 afforded the heteroatomic complexes {κ2N,O-Ar[NON]Co(μ-Cl)2Li}2 (3a, Ar = 2,6-Me2C6H3; 3b, Ar = 2,6-iPr2C6H3) or κ2N,O-Ar[NON]Co2Cl2(μ-Cl)2Li(THF)2 (4a, Ar = 2,6-Me2C6H3; 4b, Ar = 2,6-iPr2C6H3) depending on the amount of CoCl2 used. The Co(iii)/Li heterometallic complex 3b' with imino-phenoxyl-amino ligands was formed probably via a redox reaction of 3b. The reactions of Ar[NCN]Li with elemental sulfur and CoCl2 gave κ2N,S-Ar[NSN]Co2Cl2(μ-Cl)2Li(THF)2 (5a, Ar = 2,6-Me2C6H3; 5b, Ar = 2,6-iPr2C6H3) respectively. These complexes were well characterized by FT-IR and elemental analyses, and the molecular structures of 1b', 3b', 4a, and 4b were confirmed by X-ray crystallography. Upon activation with Al2Et3Cl3 in toluene, these complexes showed high activities in isoprene polymerization affording cis-1,4 enriched polymers with a moderate molecular weight (0.85-4.72 × 104 Da).