title: Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides.
abstract: The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM=B=N=CR2](+), which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)2B(Cl)NCAr2 (Ar = p-Tol/Mes, 5c/d) have been generated by B-centred substitution chemistry using CpFe(CO)2BCl2 and suitable lithiated ketimines - a reaction which is found to be highly sensitive to the steric bulk at both the metal fragment and the ketimino group. Carbonyl/phosphine exchange (using PCy3 or PPh3), followed by halide abstraction allows for the generation of the cationic iminoborylenes [CpFe(PR3)(CO)(BNCAr2)](+)[BAr(X)4](-) (R = Cy, Ar = p-Tol/Mes, 12c/d; R = Ph, Ar = Mes, 13d; Ar(X) = 3,5-X2C6H3 where X = Cl, CF3) which have been characterized spectroscopically and by X-ray crystallography. The reactivity of these iminoborylene systems towards a range of nucleophiles and unsaturated substrates has been investigated. The latter includes the first examples of M=B metathesis reactivity with a carbodiimide, and results in Fe=B cleavage and formation of the isonitrile complexes [CpFe(PCy3)(CO)(CNR)](+)[BAr(Cl)4](-) (R = (i)Pr/Cy, 16/17).
authors.affiliation: Institute of Organic Chemistry, Department of Chemistry, University of Duisburg-Essen, Universitätsstrasse 7, 45141 Essen, Germany. jochen.niemeyer@uni-due.de.
authors.forename: J
authors.initials: J
authors.lastname: Niemeyer
authors.forename: M J
authors.initials: MJ
authors.lastname: Kelly
authors.forename: I M
authors.initials: IM
authors.lastname: Riddlestone
authors.forename: D
authors.initials: D
authors.lastname: Vidovic
authors.forename: S
authors.initials: S
authors.lastname: Aldridge