88610-52-0

Upstream product

• 109787-02-2 HN(C₂H₅)3⁽¹⁺⁾*HFe₃(CO)9CCH₂^(1-)=(HN(C₂H₅)3)(HFe₃(CO)9CCH₂) 
• 672-66-2 Dimethyl(phenyl)phosphine 
• 112220-73-2 Fe3(μ3-methylidenemethylether)2(carbonyl)9 
• 22560-16-3 lithium triethylborohydride 

Downstream Products

• 110935-15-4 (iron)2(carbonyl)6{HC(phenyl)C(methyl)C(phenyl)C(phenyl)} 
• 110935-17-6 (iron)2(carbonyl)6{HC(phenyl)C(phenyl)C(methyl)} 
• 110935-13-2 (hydride)(iron)3(carbonyl)9{C(methyl)C(phenyl)CH} 

Relevant academic research and scientific papers

Organolithium reagents in metal carbonyl reduction reactions. Syntheses of HFe3(μ2-COMe)(CO)10, Fe3(μ3-COMe)2(CO)9, and Fe3(μ3-C=CH2)(CO)10

n-Butyllithium reduces the Fe3(CO)12 cluster, and on subsequent treatment with Me3OBF4 the compounds HFe3(μ2-COMe)(CO)10 (2), Fe3(μ3-COMe)2(CO)9 (3), and Fe3(μ3-C=CH2)(CO)10 (1) are formed. Similar reductions are possible with t-BuLi and PhLi. Compound 2 is thus obtained more simply and less dangerously than in a previously published procedure. Complex 3 is the first example where two μ3-methylidyne methyl ether groups are symmetrically bound to a trinuclear cluster. Synthesis of 3 from 2 is also demonstrated. Similarly, compound 3 can be converted to 1. The photochemical reactivity of 1 with H2 and with (E)-cyclooctene is described. Compounds 1 and 3 have been characterized by an X-ray structure analysis. (1: C12H2O10Fe3, orthorhombic, space group Pna21, a = 21.129 (2) A?, b = 9.079 (1) A?, c = 8.599 (1) A?, Z = 4. 3: C13H6O11Fe3, monoclinic, space group P21/n, a = 8.606 (1) A?, b = 13.955 (2) A?, c = 14.899 (1) A?, β = 92.117 (9)°, Z = 4.)

Reactions of (μ-H)3Fe3(CO)9(μ3-CCH 3). H2 displacement by CO and H2 elimination following deprotonation

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.