Studies of the Mechanisms of Reactions of Binary Metal Carbonyls Page: 3
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atom for these reactions. Comparison of reactivities as a
function of the metal atom with other systems involving attack
at the metal atom and at the carbonyl carbon indicated that the
metal atom is the attack site. This is substantiated by the
observation that reactions between halide ligands (which are
also incapable of 7r-acceptance) and tungsten and molybdenum
hexacarbonyl proceeded by attack at the metal atom. However,
the reactivities of the halides with chromium hexacarbonyl were
less than expected. Comparison of the relative reactivities
of the halides with tungsten and chromium hexacarbonyl indicated
tungsten hexacarbonyl to be more sensitive than chromium to the
steric requirements of the ligand. Reactions of the halides
thus proceed via attack at the carbonyl carbon for chromium
The presence of a ligand-independent term in reactions
of chromium hexacarbonyl with the halides is consistent with
the commonly observed "dissociative" mechanism. Since the rate
constants for the ligand-dependent pathway are much larger than
those for the ligand-independent pathway, an "associative"
mechanism was proposed for the ligand-dependent pathway. Also,
the rate constants for the ligand-dependent term were very
dependent upon the nucleophilicities of the ligands. The
reactivities of the halide ligands with a given metal carbonyl
were seen to be consistent with their steric demands.
The reactions of iron pentacarbonyl with mercuric halides
were also investigated since the products obtained seem to
indicate attack both at the metal atom and carbonyl carbon.
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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/m1/3/: accessed November 13, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .