title: Reactions of manganese and rhenium complexes with organic azides: preparation of tetraazabutadiene derivatives.
abstract: Azide complexes [M(RN(3))(CO)(3)P(2)]BPh(4)[M = Mn, Re; R = C(6)H(5)CH(2), 4-CH(3)C(6)H(4)CH(2), C(6)H(5), 4-CH(3)C(6)H(4), C(5)H(9); P = PPh(OEt)(2), PPh(2)(OEt)] were prepared by allowing tricarbonyl MH(CO)(3)P(2) hydride complexes to react first with Brønsted acid (HBF(4), CF(3)SO(3)H) and then with organic azide in the dark. In sunlight the reaction yielded tetraazabutadiene [M(eta(2)-1,4-R(2)N(4))(CO)(2)P(2)]BPh(4) complexes or, with benzyl azide, imine [M{eta(1)-NH[double bond, length as m-dash]C(H)Ar}(CO)(3)P(2)]BPh(4)(Ar = C(6)H(5), 4-CH(3)C(6)H(4)) derivatives. Tetraazabutadiene [M(eta(2)-1,4-R(2)N(4))(CO)(2)P(2)]BPh(4) complexes were also prepared by reacting dicarbonyl MH(CO)(2)P(3) species first with Brønsted acid and then with an excess of organic azide. Complexes were characterised spectroscopically (IR, (1)H, (31)P, (13)C, (15)N NMR data) and by the X-ray crystal structure determination of complex [Re{eta(2)-1,4-(C(6)H(5)CH(2))(2)N(4)}(CO)(2){PPh(OEt)(2)}(2)]BPh(4)(). Strong evidence for coordination of the organic azide was obtained from the (15)N NMR spectra of labelled [M(C(6)H(5)CH(2)(15)NN(15)N)(CO)(3)P(2)]BPh(4) derivatives.
authors.affiliation: Dipartimento di Chimica, Università Ca'Foscari di 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: Alessia
authors.initials: A
authors.lastname: Bacchi
authors.forename: Alessandro
authors.initials: A
authors.lastname: Celebrin
authors.forename: Giancarlo
authors.initials: G
authors.lastname: Pelizzi
authors.forename: Gianluigi
authors.initials: G
authors.lastname: Zanardo