Ruthenium Tris(pyrazolyl)borate Diazo Complexes: Preparation of Aryldiazenido, Aryldiazene, and Hydrazine Derivatives

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Abstract
Tris(pyrazolyl)borate aryldiazenido complexes [RuTpLL'(ArN(2))](BF(4))(2) (1-3) [Ar = C(6)H(5), 4-CH(3)C(6)H(4); Tp = hydridotris(pyrazolyl)borate; L = P(OEt)(3) or PPh(OEt)(2), L' = PPh(3); L = L' = P(OEt)(3)] were prepared by allowing dihydrogen [RuTp(eta(2)-H(2))LL'](+) derivatives to react with aryldiazonium cations. Spectroscopic characterization (IR, (15)N NMR) using the (15)N-labeled derivatives strongly supports the presence of a linear [Ru]-NN-Ar aryldiazenido group. Hydrazine complexes [RuTp(RNHNH(2))LL']BPh(4) (4-6) [R = H, CH(3), C(6)H(5), 4-NO(2)C(6)H(4); L = P(OEt)(3) or PPh(OEt)(2), L' = PPh(3); L = L' = P(OEt)(3)] were also prepared by reacting the [RuTp(eta(2)-H(2))LL'](+) cation with an excess of hydrazine. The complexes were characterized spectroscopically (IR and NMR) and by X-ray crystal structure determination of the [RuTp(CH(3)NHNH(2))[P(OEt)(3)](PPh(3))]BPh(4) (4d) derivative. Tris(pyrazolyl)borate aryldiazene complexes [RuTp(ArN=NH)LL']BPh(4) (7-9) (Ar = C(6)H(5), 4-CH(3)C(6)H(4)) were prepared following three different methods: (i). by allowing hydride species RuHTpLL' to react with aryldiazonium cations in CH(2)Cl(2); (ii). by treating aryldiazenido [RuTpLL'(ArN(2))](BF(4))(2) with LiBHEt(3) in CH(2)Cl(2); (iii). by oxidizing arylhydrazine [RuTp(ArNHNH(2))LL']BPh(4) complexes with Pb(OAc)(4) in CH(2)Cl(2) at -30 degrees C. Methyldiazene complexes [RuTp(CH(3)N=NH)LL']BPh(4) were also prepared by the oxidation of the corresponding methylhydrazine [RuTp(CH(3)NHNH(2))LL']BPh(4) with Pb(OAc)(4).

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