Influence of the rac–meso isomerization of seven-membered cyclic bisphosphines on the predominant formation of chelate complexes. (4th November 2015)

• Record Type: Journal Article
• Authors: Musina, Elvira I.; Wittmann, Tatiana I.; Strelnik, Igor D.; Naumova, Olga E.; Karasik, Andrey A.; Krivolapov, Dmitry B.; Islamov, Daut R.; Kataeva, Olga N.; Sinyashin, Oleg G.; Lönnecke, Peter; Hey-Hawkins, Evamarie
• Is Part Of: Polyhedron. Volume 100(2015)
• Page Start: 344
• Page End: 350
• Publication Date: 2015-11-04
• Subjects: Heterocycles -- Bisphosphines -- Isomerization -- Platinum -- P, P-chelate; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2015.08.033
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Novel seven-membered cyclic bisphosphines have been synthesized by Mannich-like condensation as a mixture of rac and meso stereoisomers. Potentially catalytic active P, P-chelate complex is exclusively formed by slow addition of metal to the isomeric mixture of ligand. Abstract: The seven-membered cyclic bisphosphines3 –5 were synthesized by a Mannich-like condensation reaction of 1, 2-bis(phenylphosphino)ethane, formaldehyde and primary amines ( tert -butylamine, 1, 1-(diphenyl)methylamine, (2 R )-tetrahydro-2-furanylmethylamine) as a mixture of R P R P / S P S P ( rac, 3a –5a ) and R P S P ( meso, 3b –5b ) stereoisomers. The structures of the rac stereoisomers3a –5a were investigated by X-ray crystal structure analyses. The RR / SS to RS isomerization of3 –5 and oxidation processes of4 in solution were studied. Platinum(II) P, P-chelate complexes are formed exclusively from rac / meso mixtures of3 –5 .