Reactivity studies on [Cp'FeI]2: monomeric amido, phenoxo, and alkyl complexes.
A series of monomeric mono(cyclopentadienyl) iron amido, phenoxo, and alkyl complexes were synthesized, and their structure and reactivity are presented. The iron(II) centers in these 14VE one-legged piano stool complexes are high spin (S = 2) in solid state and solution independent of solvent. The silylamide compound [Cp'FeN(SiMe(3))(2)] (2a, Cp' = 1,2,4-(Me(3)C)(3)C(5)H(2)) is an excellent starting material for the reaction with more acidic substrates such as phenols. Sterically encumbered phenols 2,6-(Me(3)C)(2)(4-R)C(6)H(2)OH (R = H, Me, and tBu) were investigated. In all cases monomeric iron phenoxo half-sandwich complexes [Cp'FeOR'] (4-R) are initially formed. Rearrangement of 4-R to the diamagnetic oxocyclohexadienyl complex [Cp'Fe(η(5)-O═C(6)H(2)R'(2)R")] (5-R) is observed for 2,6-(Me(3)C)(2)(4-R)C(6)H(2)OH (R = H and Me) and the Gibbs free enthalpy of activation (ΔG(‡)) was determined. In contrast this rearrangement is inhibited when the 4-position is blocked by a tBu group. Removing the steric bulk from the 2,6-positions leads to the formation of a μ-phenoxo dimer, [Cp'Fe(μ-OC(6)H(3)tBu(2)-3,5)](2) (5). Density functional theory (DFT) was used to further elucidate the structure-reactivity relationship in these molecules. The one-legged piano stool anilido complex [Cp'Fe(NHC(6)H(2)tBu(3)-2,4,6)] (7) is not accessible via acid-base reaction between 2a and H(2)NC(6)H(2)tBu(3)-2,4,6, but can be prepared by conventional salt metathesis reaction from [Cp'FeI](2) and [Li(NHC(6)H(2)tBu(3)-2,4,6)(OEt(2))](2). In contrast, reaction of 2a with Ph(2)NH yields the bimetallic [Cp'Fe(N,C-κ(1),η(5)-C(6)H(5)NPh)Fe(N-κ(1)-NPh(2))Cp'] (8) which combines two iron centers in the same oxidation state (+2), but different spin-states (S = 0 and S = 2) which is reflected in very different Cp(cent)-Fe distances of 1.68 and 2.04 Å, respectively. A monomeric iron alkyl half-sandwich complex [Cp'FeCH(SiMe(3))(2)] (9) was prepared that exhibits no reactivity toward H(2), C(2)H(4) or N(2)O. This behavior might be rationalized by a spin-state induced reaction barrier. However, 9 reacts in the presence of CO to the iron acyl-complex [Cp'Fe(CO)(2)(C(O)CH(SiMe(3))(2))] (10) and with a CO/H(2) mixture [Cp'Fe(CO)(2)](2) (11) and CH(2)(SiMe(3))(2) are formed.
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany. mwalter@tu-bs.de
Marc D
MD
Walter
Peter S
PS
White
D000473:Alkanes / Q000138:chemical synthesis / Q000737:chemistry*; D000577:Amides / Q000138:chemical synthesis / Q000737:chemistry*; D000813:Anilides / Q000138:chemical synthesis / Q000737:chemistry; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D010636:Phenols / Q000138:chemical synthesis / Q000737:chemistry*
D000473:Alkanes; D000577:Amides; D000813:Anilides; D005296:Ferrous Compounds; D010636:Phenols