863608-79-1Relevant academic research and scientific papers
Crossover studies of methyl migration from oxygen to iron in the iron-manganese methoxycarbyne complex Cp(CO)Fe(μ-COCH 3)(μ-CO)Mn(CO)MeCp
Hersh, William H.,Fong, Raymond H.
, p. 4179 - 4189 (2008/10/09)
Thermal decomposition of the iron-manganese methoxycarbyne Cp(CO)Fe(μ-CO)(μ-COCH3)Mn(CO)MeCp (1a) occurs to give MeCpMn(CO)3 and in low yield CpFe(CO)2CH3; in the presence of PPh3, CpFe(CO)(PPh3)CH3 (2a) forms in high yield. The reaction is first-order in carbyne, but a side reaction that is also first-order in phosphine occurs to give [Cp(CO)Fe(μ-CO)2Mn(CO)MeCp]-[CH3PPh 3]+ (3a) as a byproduct. Crossover experiments between la and its bis-MeCp, CD3 analogue 1b-d3 result in scrambling of the methoxycarbyne methyl label between the products 2a and the MeCp analogue 2b. No alkyl exchange is seen in recovered starting materials in the reaction between 1a and bis-MeCp analogue 3b or (except after prolonged reaction) between the products 2a and 2b-d3. Control crossover experiments between 1a and 2b-d3 give complete alkyl scrambling. The data prove that alkyl exchange occurs among products after carbyne decomposition and presumably is induced by an intermediate that is formed by carbyne decomposition. Previous results show that the 16-electron intermediate CpFe(CO)CH3 forms at essentially the same rate from 2a as from la, ruling it out as the exchange intermediate since 2a and 2b-d 3 undergo only very slow exchange. A speculative proposal for the reactive intermediate is that it is the isomeric terminal methoxycarbyne CpFe≡COCH3, and alkyl migration from oxygen to iron occurs after cluster cleavage. A detailed kinetic scheme for alkyl scrambling is proposed and tested by computer modeling: using an iterative procedure that couples numerical integration of the proposed rate equations with a simplex minimization algorithm designed to find the best rate constants, concentration data from several runs could be quantitatively fit to the proposed mechanism.
