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Published on: March 20, 2017
Monomeric Fe(iii) half-sandwich complexes [Cp'FeX2] - synthesis, properties and electronic structure
Matthias Reiners1, Miyuki Maekawa1, Dirk Baabe1
1Technische Universität Braunschweig, Institut für Anorganische und Analytische Chemie, Hagenring 30, 38106 Braunschweig, Germany. mwalter@tu-bs.de.
Abstract:
The half-sandwich complex [Cp'Fe(μ-I)]2 (1; Cp' = η5-1,2,4-(Me3C)3C5H2) is cleaved when heated in toluene to form a cation-anion pair [{Cp'Fe(η6-toluene)}+{Cp'FeI2}-] (2), in which the two Fe(ii) atoms adopt different spin states, i.e., a low-spin (S = 0) and a high-spin (S = 2) configuration. Upon oxidation of 1 with C2H4I2, the thermally stable 15VE species [Cp'FeI2] (3) can be isolated, in which the Fe(iii) atom adopts an intermediate spin (S = 3/2) configuration. Complex 3 is an excellent starting material for further functionalizations and it reacts with Mg(CH2SiMe3)2 to form the unprecedented Fe(iii) (S = 3/2) bis(alkyl) complex [Cp'Fe(CH2SiMe3)2] (4). The respective spin states of complexes 2-4 are confirmed by single-crystal X-ray crystallography, zero-field 57Fe Mössbauer spectroscopy, and solid-state magnetic susceptibility measurements. In contrast to the related 14VE high-spin (S = 2) Fe(ii) alkyl species [Cp'FeCH(SiMe3)2], which resists the reaction with H2 as a consequence of a spin-induced reaction barrier, complex 4 reacts cleanly with H2 (8 bar) in cyclohexane to yield iron hydrides [{Cp'Fe}2(μ-H)3] (5) and [Cp'Fe(μ-H)2]2 (6) in a 1 : 4 ratio. However, when the hydrogenation of 4 is carried out in benzene, a green 19VE [Cp'Fe(η6-C6H6)] (A) intermediate is formed, which dimerizes to the bis(cyclohexadienyl)-bridged product [(Cp'Fe)2(μ2-η5:η5-C12H12)] (7). Further evidence for the intermediacy of [Cp'Fe(η6-C6H6)] (A) was gathered by X-band EPR and UV/vis spectroscopy. Interestingly, attempts to oxidize 7 with AgSbF6 proceeded via C-C bond cleavage instead of metal oxidation to form [Cp'Fe(C6H6)][SbF6] (8).
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