Wednesday 1 April 2015

inorganic chemistry - Predicting bond-strength of metal carbonyls



The metal carbonyls (and similar organometallic compounds) involve a combination of sigma bond, a pi bond and backbonding. The bond strengths under consideration are the metal-carbon bond and the carbon oxygen bond. Here is the original question:-



Predict the order of $\ce{C-O}$ bond strength in the following:-
I) $[\ce{Mn(CO)_6}]^+$
II) $[\ce{Cr(CO)_6}]$
III) $[\ce{V(CO)_6}]^-$



All of these are isoelectronic, and hence whatever the difference of bond strengths, must arise from the difference in the resultant nuclear force of attraction. Since $\ce{Mn+}$ has the highest charge density, I would assume that the $\ce{M-C}$ bond strength of the manganese compound is the strongest (vanadium being the weakest) and therefore, the $\ce{C-O}$ bond strength must follow the opposite order, as the strengthening of the metal carbonyl bond should weaken the carbon oxygen bond.


But the answer given is III, exactly the opposite of my prediction. Why is it so? A relevant factor which I didn't consider is the back bonding, but I am unsure of how to integrate that into my prediction. Also, how would we make a prediction if the given compounds were not isoelectronic?




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