Premium
[Cp 2 Mo(OH)(OH 2 )] + ‐Catalyzed Hydrolysis of Mono‐ and Difunctional Ethers: Theoretical Understanding of Their Divergent Reactivity
Author(s) -
Álvarez Daniel,
CastroLópez Elena,
FernándezPulido Yoana,
Menéndez M. Isabel,
López Ramón
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900513
Subject(s) - chemistry , ether , reactivity (psychology) , catalysis , vinyl ether , hydrolysis , nucleophile , medicinal chemistry , diethyl ether , reaction mechanism , polymer chemistry , organic chemistry , copolymer , medicine , alternative medicine , pathology , polymer
The reaction mechanism of [Cp 2 Mo(OH)(OH 2 )] + ‐catalyzed hydrolysis of ethyl vinyl, divinyl, and diethyl ethers was theoretically investigated. The reaction pathway evolving through the coordination of the ether oxygen to Mo is notably disfavored, as experimentally suggested. This is the only operative coordination mode for diethyl ether and explains why this monofunctional ether is not hydrolyzed by molybdocenes. However, difunctional ethers containing a functionality susceptible to activation like the vinyl group present an alternative reaction pathway proceeding through the coordination of the vinyl terminal carbon to Mo with accessible rate‐determining Gibbs energy barriers of 29.3 kcal/mol (divinyl ether) and 22.2 kcal/mol (ethyl vinyl ether). In these cases, the catalyst withdraws electron density from the unsaturated bonds and prepares the group for an easy OH‐nucleophilic attack. This explains the molybdocene‐catalyzed hydrolysis of ethyl vinyl ether experimentally observed and, more interestingly, reveals what the crucial role of the functional groups linked to the ether oxygen really is in the viability of these reactive processes.