title: Improved Catalytic Activity and Stability of a Palladium Pincer Complex by Incorporation into a Metal-Organic Framework.
abstract: A porous metal-organic framework Zr6O4(OH)4(L-PdX)3 (1-X) has been constructed from Pd diphosphinite pincer complexes ([L-PdX](4-) = [(2,6-(OPAr2)2C6H3)PdX](4-), Ar = p-C6H4CO2(-), X = Cl, I). Reaction of 1-X with PhI(O2CCF3)2 facilitates I(-)/CF3CO2(-) ligand exchange to generate 1-TFA and I2 as a soluble byproduct. 1-TFA is an active and recyclable catalyst for transfer hydrogenation of benzaldehydes using formic acid as a hydrogen source. In contrast, the homogeneous analogue (t)Bu(L-PdTFA) is an ineffective catalyst owing to decomposition under the catalytic conditions, highlighting the beneficial effects of immobilization.
authors.affiliation: Department of Chemistry, Brandeis University , 415 South Street MS 015, Waltham, Massachusetts 02453, United States.
authors.forename: Samantha A
authors.initials: SA
authors.lastname: Burgess
authors.affiliation: Department of Chemistry, Brandeis University , 415 South Street MS 015, Waltham, Massachusetts 02453, United States.
authors.forename: Abebu
authors.initials: A
authors.lastname: Kassie
authors.affiliation: Department of Chemistry, Brandeis University , 415 South Street MS 015, Waltham, Massachusetts 02453, United States.
authors.forename: Sarah A
authors.initials: SA
authors.lastname: Baranowski
authors.affiliation: Department of Chemistry, Brandeis University , 415 South Street MS 015, Waltham, Massachusetts 02453, United States.
authors.forename: Keith J
authors.initials: KJ
authors.lastname: Fritzsching
authors.affiliation: Department of Chemistry, Brandeis University , 415 South Street MS 015, Waltham, Massachusetts 02453, United States.
authors.forename: Klaus
authors.initials: K
authors.lastname: Schmidt-Rohr
authors.affiliation: Center for Neutron Research, National Institute of Standards and Technology , Gaithersburg, Maryland 20899, United States.|Chemical and Biomolecular Engineering, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Craig M
authors.initials: CM
authors.lastname: Brown
authors.affiliation: Department of Chemistry, Brandeis University , 415 South Street MS 015, Waltham, Massachusetts 02453, United States.
authors.forename: Casey R
authors.initials: CR
authors.lastname: Wade