PS3_ANSWERS_2018.pdf - CHEM 4571 u2013 Organometallic...

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CHEM 4571 – Organometallic Chemistry, Spring 2018 Problem Set 3 Due Date – Beginning of Lecture on Thursday, March 15 th 2018 1) CO Substitution a) Fe(CO) 5 substitutes CO very slowly, typically through a dissociative mechanism. In the presence of an acid, substitution is greatly accelerated. Justify this observation.
b) For dissociative CO substitutions, the rate tends to be higher as the (CO) stretching frequency of the carbonyl increases. Suggest a reason.
c) Choose the metal complex that will most readily perform one CO ligand substitution with PMe 3 and briefly and clearly state your reasoning. 3
ii) ( 4 -butadiene)Fe(CO) 3 – or – ( 4 -cyclobutadiene)Fe(CO) 3
iii) W(CO) 4 (PEt 3 ) 2 – or – [Rh(CO) 2 (dmpe)] + The W complex is 18 e and saturated, while the Rh complex is 16 e and has an open, accessible empty orbital.

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