Studies of the Mechanisms of Reactions of Binary Metal Carbonyls Page: 4
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The reactions are oxidative elimination reactions which involve
an increase by one in the coordination number of the metal.
The investigation of the reaction with mercuric chloride
indicated the formation of the previously unobserved product,
Fe(C0) ^ (H^Clg) . The rate of disappearance of Fe(CO)g varied
directly with the square of the ligand concentration, a fact
consistent with mechanisms proposed for other oxidative
elimination reactions. Such a mechanism involves the successive
formation of 1:1 and 1:2 "adducts" of substrate and ligands.
The 1:2 adduct then decomposes to form the product, Fe(CO)^-
(HgCl)25 and phosgene gas. The structure of a related complex
suggests for the 1:2 adduct a structure which would allow for a
carbonyl ligand to abstract two chlorine groups from the compound
to lead to phosgene. This mechanism involving attack at the
carbonyl carbon is plausible since the mercuric halide
substituents on iron would be expected to cause an electron
deficiency in the carbon atom.
The rate of formation of the final product was seen to
be dependent upon the square of the mercuric halide concentration.
Therefore, the conversion of Fe(CO)^(HgX)^ "to the final product
was proposed to proceed by the successive abstraction by each
HgX group of two molecules of mercuric halide. These oxidative
elimination reactions are related to a chemical model for
the intermediate step in the reduction of dinitrogen to ammonia
and their similarities and differences are discussed.
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Pardue, Jerry E. Studies of the Mechanisms of Reactions of Binary Metal Carbonyls, dissertation, May 1977; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc332386/m1/4/: accessed November 12, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .