title: Addition of a phosphinidene complex to C=N bonds: P-ylides, azaphosphiridines, and 1,3-dipolar cycloadditions.
abstract: The terminal phosphinidene complex PhPW(CO)5 adds to the imine bond of PhHC=N-Ph to give 3-membered ring azaphosphiridines, which undergo ring-expansion with an additional imine to yield a set of four isomeric five-membered ring diazaphospholanes. Treatment with the diimines PhHC=N-(CH2)n-N=CHPh (n=2,3,4) results instead-in all three cases-in only a single isomer of the (CH2)n bridged diazaphospholane. For n=2 or 3, this aminal group is easily hydrolyzed to afford new 6- and 7-membered ring heterocycles. No intermediate azaphosphiridine complex is observed during the addition reaction to the diimines. B3LYP/6-31G* calculations on an unsubstituted, uncomplexed system suggest that the initially formed P,N-ylide of the H2C=N-(CH)2-N=CH2 diimine both kinetically and thermodynamically favors an intramolecular 1,3-dipolar cycloaddition over an imine insertion into the CPN ring of an intermediate azaphosphiridine. Single-crystal X-ray structures for the (CH2)2-bridged azaphospholane complex and the HCl adduct of the 7-membered hydrolysis product are presented.
authors.affiliation: Department of Organic and Inorganic Chemistry, Faculty of Sciences, Vrije Universiteit, Amsterdam, The Netherlands.
authors.forename: M J
authors.initials: MJ
authors.lastname: Vlaar
authors.forename: P
authors.initials: P
authors.lastname: Valkier
authors.forename: F J
authors.initials: FJ
authors.lastname: de Kanter
authors.forename: M
authors.initials: M
authors.lastname: Schakel
authors.forename: A W
authors.initials: AW
authors.lastname: Ehlers
authors.forename: A L
authors.initials: AL
authors.lastname: Spek
authors.forename: M
authors.initials: M
authors.lastname: Lutz
authors.forename: K
authors.initials: K
authors.lastname: Lammertsma