Mono- and binuclear aryldiazenido complexes [Fe(ArN(2))(CO)(2)P(2)]BPh(4) (1-4) and [{Fe(CO)(2)P(2)}(2)(&mgr;-N(2)Ar-ArN(2))](BPh(4))(2) (5-8) [P = P(OEt)(3), PPh(OEt)(2), PPh(2)OEt, P(OPh)(3); Ar = C(6)H(5), 2-CH(3)C(6)H(4), 4-CH(3)C(6)H(4); Ar-Ar = 4,4'-C(6)H(4)-C(6)H(4), 4,4'-(2-CH(3))C(6)H(3)-C(6)H(3)(2-CH(3)), 4,4'-C(6)H(4)-CH(2)-C(6)H(4)] were prepared by allowing hydride species FeH(2)(CO)(2)P(2) to react with an excess of mono- (ArN(2))(BF(4)) or bis-aryldiazonium (N(2)Ar-ArN(2))(BF(4))(2) salts, respectively, at low temperature. A reaction path involving a hydride-aryldiazene intermediate [FeH(ArN=NH)(CO)(2)P(2)](+), which, through the loss of H(2), affords the final aryldiazenido complexes 1-8, is proposed. The compounds were characterized by (1)H and (31)P{(1)H} NMR spectroscopy (including (15)N isotopic substitution) and X-ray crystal structure determination. The complex [Fe(CO)(2){P(OEt)(3)}(2){&mgr;-4,4'-N(2)(2-CH(3))C(6)H(3)-C(6)H(3)(2-CH(3))N(2)}](BPh(4))(2) (5b) crystallizes in the space group P&onemacr; with a = 15.008(4) Å, b = 17.094(5) Å, c = 10.553(3) Å, alpha = 99.56(1) degrees, beta = 102.80(1) degrees, gamma = 65.30(1) degrees, and Z = 1. The structure is centrosymmetric and consists of binuclear cations with the two iron atoms in a quite regular trigonal bipyramidal environment, with the two CO in the equatorial and the two phosphites in the apical position, respectively. Aryldiazenido complexes 1-8 react with strong acids HX (X = Cl, CF(3)SO(3), CF(3)CO(2)) to give the corresponding aryldiazene derivatives, according to the equilibrium [Fe(ArN(2))(CO)(2)P(2)](+) + HX right harpoon over left harpoon [FeX(ArN=NH)(CO)(2)P(2)](+). Electrochemical studies of both mono- (1-4) and binuclear (5-8) compounds were undertaken, and a mechanism for oxidation and reduction processes is proposed.

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The deactivation of a nickel reforming catalyst during the upgrading of the producer gas obtained by gasification of lignocellulosic biomass was studied. The research involved several steps: the selective deactivation of the catalyst in a laboratory scale; the streaming of the catalyst with the producer gas of a downdraft and an oxygen/steam circulating fluidized bed (CFB) gasifier; and tests in a reformer placed in a slipstream of the CFB gasifier. The information obtained allowed to elucidate the catalyst deactivation mechanisms taking place during the reforming of the producer gas: physical deactivation by deposition of fine ashes, aerosol particulate or carbon; poisoning by H 2 S and HCl present in the gas phase and thermal sintering because of the high operation temperatures required to avoid the chemical deactivation. These physical and chemical effects depended on the composition of the biomass fuel.

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