109838-63-3Relevant academic research and scientific papers
Reactions of (μ-H)3Fe3(CO)9(μ3-CCH 3). H2 displacement by CO and H2 elimination following deprotonation
Dutta, Tamal K.,Meng, Xiangsheng,Vites, Jose C.,Fehlner, Thomas P.
, p. 2191 - 2200 (2008/10/08)
The conversion of (μ-H)3Fe3(CO)9(μ3-CCH 3) (I) to (μ-H)Fe3(CO)9(μ-CO)CCH3 (II) and the reverse reaction have been carried out via both direct and indirect routes. Direct H2 displacement by CO and the reverse occur at 60°C and 1-4 arm of pressure in an equilibrium process for which the equilibrium constant has been measured. The indirect route involves deprotonation of I in a reaction which is first order in I and first order in base. This is followed by a spontaneous, first-order cluster oxidation via H2 elimination from an intermediate anion to yield [(μ-H)Fe3(CO)9(CCH2)]- (III). Protonation of III followed by CO addition leads to II. On the other hand, protonation in the presence of H2 at 1 atm of pressure leads to reduction of cluster III to I. These reactions are probed with isotopic labeling experiments that serve to define the mechanism for the indirect route relative to sites of deprotonation and dehydrogenation. Spectroscopic and kinetic evidence for the existence of intermediates in both processes is presented.
