title: Diazoalkane complexes of ruthenium with tris(pyrazolyl)borate and bis(pyrazolyl)acetate ligands.
abstract: Diazoalkane complexes [Ru(Tp)(N2CAr1Ar2)(PPh3)L]BPh4 ( and ) [Tp = tris(pyrazolyl)borate; L = P(OMe)3, P(OEt)3; Ar1 = Ar2 = Ph; Ar1 = Ph, Ar2 = p-tolyl; Ar1Ar2 = C12H8] were prepared by allowing chloro-compounds RuCl(Tp)(PPh3)L to react with diazoalkane in the presence of NaBPh4. Acrylonitrile CH2[double bond, length as m-dash]C(H)CN reacts with diazoalkane complexes to give 3H-pyrazole derivatives [Ru(Tp){N[double bond, length as m-dash]NC(Ar1Ar2)CH(CN)CH2}(PPh3){P(OMe)3}]BPh4 and [Ru(Tp){N[double bond, length as m-dash]NC(Ar1Ar2)CH2C(H)CN}(PPh3){P(OMe)3}]BPh4 (). Diazoalkane complexes [Ru(bpza)(N2CAr1Ar2)(PPh3)2]BPh4 () [bpza = bis(pyrazolyl)acetate] were also prepared. All complexes were characterised by IR and NMR spectroscopy and X-ray crystal structure determination of [Ru(Tp){N2C(Ph)(p-tolyl)}(PPh3){P(OMe)3}]BPh4 (). The differences exhibited by [Ru(Tp){N2C(Ph)(p-tolyl)}(PPh3){P(OMe)3}](+) and [Ru(Cp){N2C(Ph)(p-tolyl)}(PPh3){P(OMe)3}](+), as regards coordination of the diazoalkane ligand and reactivity towards alkenes, were explained on the basis of a comparative DFT study.
authors.affiliation: Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, Dorsoduro 2137, 30123 Venezia, Italy. albertin@unive.it.
authors.forename: Gabriele
authors.initials: G
authors.lastname: Albertin
authors.forename: Stefano
authors.initials: S
authors.lastname: Antoniutti
authors.forename: Marco
authors.initials: M
authors.lastname: Bortoluzzi
authors.forename: Jesús
authors.initials: J
authors.lastname: Castro
authors.forename: Lidia
authors.initials: L
authors.lastname: Marzaro