Articles publicats en revistes (Institut de Nanociència i Nanotecnologia (IN2UB))

monitor the binding. The binding affinity of PtL2 for MTOA·Cl is 2-fold smaller than that of the C[4]P precursor. This difference is attributed to dissimilar anion−π interactions and binding geometries in the ion-paired complexes of the two receptors, (Cl⊂PtL2/C[4]P)@MTOA. Isothermal titration calorimetry (ITC) experiments revealed subtle differences in enthalpy and entropy. The entropic term, although negative, was very small, suggesting the relevance of the dissociation/association processes of the salt and the ion-paired complexes. We investigated the binding selectivity of PtL2 toward a series of halides in acetone solution favoring ion-pair dissociation. PtL2 binds chloride selectively and with a high affinity, producing mainly an anionic complex.

Active catalysts derived from cobalt and the Xantphos ligand were synthesised, characterised and tested in the

hydroformylation of pure linear alkenes or their mixtures. The preformed complex [Co2(CO)6(Xantphos)] showed similar

reactivity and selectivity towards aldehydes as the active catalyst formed in situ from equimolar amounts of [Co2(CO)8] and

Xantphos. In the case of oct-1-ene, the linear aldehyde was obtained with good chemo- and regio-selectivity (linear to

branched ratio was up to 75:25). For all octene isomers, tandem isomerisation-hydroformylation processes took place.

Regioselectivities for all the studied octene isomers remained practically constant, independently of the position or

geometry of the CC double bond in the starting material. Moreover, by-products were formed in similarly small amounts

for all the octene isomers. We also demonstrated that this chemistry is an interesting strategy for valorising mixtures of

linear hexenes, heptenes or octenes by transforming the initial mixture into one major aldehyde (addition of a CHO group

to the C1 carbon of the alkene skeleton, up to 73% selectivity). Moreover, these mixtures of alkenes were hydroformylated

with low final amounts of non-hydroformylated alkenes, hydrogenated alkenes and alcohols.