100112-75-2Relevant academic research and scientific papers
Iron(II) aryldiazene complexes: Preparation, characterization, and ligand-substitution reactions with ketones, nitriles, and isocyanides. Crystal structure of the diazene precursor, the new hydride trans-[FeH(CO){P(OEt)3}4]BPh4
Albertin, Gabriele,Antoniutti, Stefano,Lanfranchi, Maurizio,Pelizzi, Giancarlo,Bordignon, Emilio
, p. 950 - 957 (2008/10/08)
Contribution from the Dipartimento di Chimica, Università di Venezia, 30123 Venice, Italy, and the Istituto di Chimica Generale ed Inorganica, Centro di Studio per la Strutturistica Diffrattometrica del CNR, Università di Parma, 43100 Parma, Italy Iron hydride complexes, trans-[FeH(CO)L4]BPh4 (L = P(OMe)3, P(OEt)3, PhP(OEt)2), were prepared by allowing [FeX(CO)L4]+ (X = Cl, Br) derivatives to react with zinc in acetonitrile solution; the crystal structure of trans-[FeH(CO){P(OEt)3}4]BPh4 was determined. The compound crystallized in the orthorhombic space group P212121 with four molecules per unit cell and lattice parameters a = 23.658 (14) ?, b = 23.671 (13) ?, and c = 10.507 (6) ?. The structure was solved by the heavy-atom technique and refined to R = 0.0756 for 2813 independent reflections having I > 2σ(I). The environment of the iron atom is that of a distorted octahedron, the ligands being one hydride ion, one carbonyl group, and four phosphite groups. The complex [FeH(CO){P(OEt)3}4]+ undergoes insertion reactions with aryldiazonium cations to afford the first iron(II) diazene derivatives, trans-[Fe(ArNNH)-(CO)L4](BPh4)2 (Ar = 4-CH3C6H4, 4-ClC6H4). The 1H NMR spectrum of the 15N-labeled complex (J15NH = 67 Hz) excludes the existence of an arylhydrazido(2-) derivative. The reaction of these diazene compounds with ketones was examined and led to the synthesis of new O-bonded trans-[Fe(CO)(RR′CO)L4](BPh4)2 (R = R′ = CH3; R = CH3, R′ = C2H5; R = CH3, R′ = C6H5; R, R′ = (CH2)5 (cyclohexanone)) ketone complexes. Furthermore, carbonyl, isocyanide, and nitrile derivatives of the type cis-[Fe(CO)2L4](BPh4)2, cis-[Fe(CO)(RNC)L4](BPh4)2 (R = C6H5, 4-CH3C6H4, 4-CH3OC6H4, 2,6-(CH3)2C6H3, 4-NO2C6H4), and trans-[Fe(CO)(RCN)L4](BPh4)2, (R = C6H5, 4-CH3C6H4, 2-CH3C6H4, CH3, NC(CH2)4) were obtained; their characterization by infrared and 1H and 31P NMR data is also reported. The nitrile complexes show ν(CN) increased in comparison to the free-ligand value.
