Diazoalkane complexes of ruthenium with tris(pyrazolyl)borate and bis(pyrazolyl)acetate ligands.

Gabriele Albertin, Stefano Antoniutti, Marco Bortoluzzi, Jesús Castro, Lidia Marzaro

Index: Dalton Trans. 44 , 15470-80, (2015)

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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.