NEW MOLECULAR-HYDROGEN IRON(II) COMPLEXES - SYNTHESIS, CHARACTERIZATION, AND REACTIVITY WITH ARYLDIAZONIUM CATIONS

Dihydrogen complexes of the type [FeH(η2-H2)P4]BPh4[P = PhP(OEt)2 and P(OEt)3] were prepared by allowing the dihydride FeH2P4 to react at -80 °C with HBF4•Et2O in ethanol. Variable-temperature 1H and 31P{1H} NMR spectra and T1 measurements of the complexes are reported. Ligand-substitution reactions with CO, isocyanide, nitrile, and phosphite afforded the new monohydrides [FeHLP4]BPh4 [L = CO, 4-CH3C6H4NC, 4-CH3OC6H4NC, 4-ClC6H4NC, 2,6-(CH3)2C6H3NC, 4-CH3C6H4CN, CH3(CH2)2CN, P(OEt)3, and PhP(OEt)2]. Furthermore, the reactivity with aryldiazonium cations of both molecular hydrogen [FeH(η2-H2)P4] +and hydride [FeHLP4]+derivatives was examined and led to the synthesis of bis-(aryldiazenido) [Fe(ArN2)2P3]2+(Ar = 4-CH3C6H4and 4-CH3OC6H4) and monodiazene [Fe(ArN=NH)LP4]2+ (L = nitrile) complexes, respectively. Their characterization by infrared, 1H, and 31P{1H} NMR data is also reported. © 1989, American Chemical Society. All rights reserved.