Reactivity of Hydrides FeH(2)(CO)(2)P(2) (P = Phosphites) with Aryldiazonium Cations: Preparation, Characterization, X-ray Crystal Structure, and Electrochemical Studies of Mono- and Binuclear Aryldiazenido Complexes.
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.
Albertin
Gabriele
G
Dipartimento di Chimica and Dipartimento di Chimica Fisica, Università Ca' Foscari di Venezia, Dorsoduro 2137, 30123 Venezia, Italy, and Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Centro CNR di Strutturistica Diffrattometrica, Università di Parma, Viale delle Scienze, 43100 Parma, Italy.
Antoniutti
Stefano
S
Bacchi
Alessia
A
Barbera
Davide
D
Bordignon
Emilio
E
Pelizzi
Giancarlo
G
Ugo
Paolo
P