Cationic Palladium(II) Complexes of Phosphine–Sulfonamide Ligands: Synthesis, Characterization, and Catalytic Ethylene Oligomerization

• Published in: Organometallics Vol. 33; no. 14; pp. 3738 - 3745
• Main Authors: Zhang, Yanlu, Cao, Yanchun, Leng, Xuebing, Chen, Changle, Huang, Zheng
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 28.07.2014; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Physical Sciences; Science & Technology; INSERTION; POLYMERIZATION CATALYSTS; NICKEL; SUBSTITUENTS; REACTIVITY; DIMERIZATION; COORDINATION; COPOLYMERIZATION; ALKYL COMPLEXES; POLYETHYLENE
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om5004094

A series of cationic palladium­(II) complexes bearing phosphine–sulfonamide ligands, [(P,O)­PdMe­(lutidine)]­[SbF6], were synthesized and used for catalytic ethylene oligomerization. The molecular structure of the complex {[N,N-dicyclohexyl-2-(diphenylphosphanyl)­benzenesulfonamide]­PdMe­(lutidine)}­[SbF6] shows that the phosphorus atom and the oxygen atom coordinate to the palladium center. The ethylene oligomerization behavior is greatly influenced by the phosphino substituents, while the substituents on sulfonamide show only minimal effects. Complexes containing the diphenylphosphanyl group are highly selective for ethylene dimerization, affording 1-butene exclusively with moderate activity. The bulkier bis­(2-methoxyphenyl)­phosphanyl group leads to higher activity and gives α-olefins containing mainly 1-butene and 1-hexene, with a 1-hexene content of up to 35%. The palladium complexes bearing alkyl phosphino substituents give 1-butene and 1-hexene as the major products; a small amount of 2-butene (<5%) was observed, suggesting the occurrence of chain walking. The addition of B­(C6F5)3 greatly enhances the catalytic activity. Experimental results suggest that the increase in activity is likely due to the abstraction of lutidine, not from the coordination of B­(C6F5)3 to the sulfonamide oxygen atom.