186344-06-9Relevant academic research and scientific papers
Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)3(4-CH3C6H 4N=NH){PPh(OEt)2}2]BF4 and [Mn(CO)3(NH2NH2){PPh(OEt)2} 2]BPh4 Derivatives
Albertin, Gabriele,Antoniutti, Stefano,Bacchi, Alessia,Bordignon, Emilio,Busatto, Fabio,Pelizzi, Giancarlo
, p. 1296 - 1305 (2008/10/09)
Aryldiazene complexes [Mn(CO)3(ArN=NH)P2]BF4 (1, 2) and [{Mn(CO)3P2}2(μ-HN=NArArN=NH)](BF 4)2 (3, 4) [P = PPh(OEt)2, PPh2OEt; Ar = C6H5, 2-CH3C6H4, 4-CH3C6H4, 4-CH3OC6H4; ArAr = 4,4′-C6H4C6H4, 4,4′-(2-CH3)C6H3C6H 3(2-CH3), 4,4′-C6H4CH2C6H4] were prepared by reacting hydride species MnH(CO)3P2 with the appropriate aryldiazonium cations in CH2Cl2 or acetone solutions at -80 °C. The compounds were characterized by IR, 1H and 31P NMR spectra (with 15N isotopic substitution), and a single-crystal X-ray structure determination. The complex [Mn(CO)3(4-CH3C6H 4N=NH){PPh(OEt)2}2]BF4 (1c) crystallizes in the space group C2/c with a = 31.857(5) A?, b = 11.119(2) A?, c = 22.414(3) A?, β = 97.82(1)°, and Z = 8. Treatment of aryldiazene compounds 1-4 with NEt3 gave the pentacoordinate aryldiazenido [Mn(CO)2(ArN2)P2] (5, 6) and [{Mn(CO)2P2}2(μ-N2-ArArN 2)] (7, 8) [P = PPh(OEt)2, PPh2OEt; Ar = C6H5,4-CH3C6H4; ArAr = 4,4′-C6H4C6H4, 4,4′-(2-CH3)C6H3C6H 3-(2-CH3)] derivatives. Protonation reactions of these aryldiazenido complexes 5-8 with HCl afforded the aryldiazene [MnCl(CO)2(ArN=NH)P2] (9) and [{MnCl(CO)2P2}2(μ-HN=NArArN=NH)] (10) derivatives. Hydrazine complexes [Mn(CO)3(RNHNH2)P2]BPh4 (11, 12) [P = PPh(OEt)2, PPh2OEt; R = H, CH3, C6H5, 4-NO2C6H4] were prepared by allowing hydride species MnH(CO)3P2 to react first with triflic acid and then with the appropriate hydrazine. Their characterization by IR, 1H and 31P NMR spectra, and an X-ray crystal structure determination is reported. The compound [Mn(CO)3(NH2NH2){PPh(OEt)2} 2]BPh4 (11a) crystallizes in the space group P1 with a = 13.772(3) A?, b = 14.951(4) A?, c = 13.319(3) A?, α = 104.47(1)°, β = 100.32(1)°, γ = 111.08(1)°, and Z = 2. Oxidation reactions of hydrazine compounds 11 and 12 with Pb(OAc)4 at -40 °C gave stable aryldiazene [Mn(CO)3(RN=NH)P2]BPh4 and thermally unstable (upon reaching -40 °C) diazene [Mn(CO)3(HN=NH)P2]-BPh4 derivatives.
