Facile immobilization of P N N N P-Pd pincer complexes in MFU-4 l -OH and the effects of guest loading on Lewis acid catalytic activity.

A palladium diphosphine pincer complex H 3 (P N N N P-PdI) has been encapsulated in the benzotriazolate metal-organic framework MFU-4 l -OH ([Zn 5 (OH) 4 (btdd) 3 ], btdd 2- = bis(1,2,3-triazolo)dibenzodioxin), and the resulting materials were investigated as Lewis acid catalysts for cyclization of citronellal to isopulegol. Rapid catalyst immobilization is facilitated by a Brønsted acid-base reaction between the H 3 (P N N N P-PdI) benzoic acid substituents and Zn-OH groups at the framework nodes. Catalyst loading can be controlled up to a maximum of 0.5 pincer complexes per formula unit [PdI-x, Zn 5 (OH) 4- nx (btdd) 3 (H 3- n P N N N P-PdI) x x = 0.06-0.5, n ≈ 2.75]. Oxidative ligand exchange was used to replace I - with weakly coordinating BF 4 - anions at the Pd-I sites, generating the activated PdBF4-x catalysts ( x = 0.06, 0.10, 0.18, 0.40). The Lewis acid catalytic activity of the PdBF4-x series decreases with increasing catalyst density as a result of the appearance of mass transport limitations. Initial catalytic rates show that the activity of PdBF4-0.06 approaches the intrinsic activity of a homogeneous P N N N P-PdBF 4 catalyst analogue. In addition, PdBF4-0.06 exhibits better catalytic activity than the metallolinker-based MOF Zr-PdBF 4 and was not subject to leaching or catalyst degradation processes observed for the homogeneous analogue.