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Reversible Reactions of Ni and Pd Hydroxo Pincer Complexes [( i Pr PCP)M–OH] with CO 2 : Solid‐State Study of the Decarboxylation of the Monomeric Bicarbonate Complexes [( i Pr PCP)M–OCOOH] (M = Ni, Pd)
Author(s) -
MartínezPrieto Luis Miguel,
Real Concepción,
Ávila Elena,
Álvarez Eleuterio,
Palma Pilar,
Cámpora Juan
Publication year - 2013
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.201300995
Subject(s) - chemistry , decarboxylation , nickel , carbonate , bicarbonate , hydroxide , inorganic chemistry , pincer ligand , ligand (biochemistry) , pincer movement , monomer , medicinal chemistry , polymer chemistry , catalysis , organic chemistry , biochemistry , polymer , receptor
Monomeric Ni and Pd hydroxides stabilized by the i Pr PCP pincer ligand react with CO 2 to give labile terminal bicarbonate complexes that readily lose CO 2 and water to give binuclear carbonate complexes. Differential scanning calorimetry (DSC) has been used to monitor the decomposition of both bicarcabonates in the solid state. When the carbonate complexes are heated under reflux in thf in the presence of water, full decarboxylation takes place, restoring the starting hydroxides and demonstrating that CO 2 insertion is a fully reversible process. The decarboxylation of the nickel carbonate complex is completed more readily, suggesting that the reaction of the Pd hydroxide with CO 2 is more favourable than that of its nickel counterpart. This is supported by DFT calculations, which also shows that CO 2 insertion takes place through a concerted Lipscomb‐type mechanism.