TY - JOUR

T1 - Environmentally benign benzyl alcohol oxidation and C-C coupling catalysed by amide functionalized 3D Co(II) and Zn(II) metal organic frameworks

AU - Paul, Anup

AU - Martins, Luísa M.D.R.S.

AU - Karmakar, Anirban

AU - Kuznetsov, Maxim L.

AU - Novikov, Alexander S.

AU - Guedes da Silva, M. Fátima C.

AU - Pombeiro, Armando J.L.

PY - 2020/5

Y1 - 2020/5

N2 - The new 3D metal-organic frameworks (MOFs) [Co(1κN;2κOO′-μ-L)2]n.4n(DMF).1.5n(H2O) (1) and [Zn2(1κN;2κO-μ-L)2(κO4-μ4-BTC)]n.3n(DMF).2n(H2O) (2) [L = 4-(pyridin-4-ylcarbamoyl)benzoate; BTC = benzene-1,3,5-tricarboxylate] have been synthesized from the pyridyl amide functionalized benzoic acid (HL). They were characterized by elemental, FT-IR, powder X-ray and single crystal X-ray diffraction analyses. Topological analysis of 1 discloses a 2,3,7-connected trinodal net with a 4-connected uninodal net with 2-fold interpenetrating networks, whereas that of 2 shows a dia topology. The solid-state photoluminescent properties of HL and 2 were also investigated. The heterogeneous catalytic activity of 1 and 2, under eco-friendly conditions, was assessed in benzyl alcohol oxidation and C-C bond formation model reactions. 1 has good activity in the solvent-free microwave-assisted oxidation of benzyl alcohol to benzaldehyde using tert-butyl hydroperoxide (tBuOOH, TBHP) as oxidizing agent (yields up to 89%). Although with a lower activity, MOF 2 with a redox inactive Zn(II) site, also catalyses such alcohol oxidation, which is explained by DFT calculations according to a mechanism of a similar type to that followed by the peroxidative alkane oxidation. 2 is the most active one in the ambient temperature sonochemical Knoevenagel condensation of benzaldehyde and malononitrile (yields up to 94%) and in the ambient temperature Henry C-C coupling reaction of benzaldehyde with nitroethane in water (yields > 99%), showing appreciable diastereoselectivity towards the syn isomer. The recyclability of catalysts 1 and 2 was evaluated.

AB - The new 3D metal-organic frameworks (MOFs) [Co(1κN;2κOO′-μ-L)2]n.4n(DMF).1.5n(H2O) (1) and [Zn2(1κN;2κO-μ-L)2(κO4-μ4-BTC)]n.3n(DMF).2n(H2O) (2) [L = 4-(pyridin-4-ylcarbamoyl)benzoate; BTC = benzene-1,3,5-tricarboxylate] have been synthesized from the pyridyl amide functionalized benzoic acid (HL). They were characterized by elemental, FT-IR, powder X-ray and single crystal X-ray diffraction analyses. Topological analysis of 1 discloses a 2,3,7-connected trinodal net with a 4-connected uninodal net with 2-fold interpenetrating networks, whereas that of 2 shows a dia topology. The solid-state photoluminescent properties of HL and 2 were also investigated. The heterogeneous catalytic activity of 1 and 2, under eco-friendly conditions, was assessed in benzyl alcohol oxidation and C-C bond formation model reactions. 1 has good activity in the solvent-free microwave-assisted oxidation of benzyl alcohol to benzaldehyde using tert-butyl hydroperoxide (tBuOOH, TBHP) as oxidizing agent (yields up to 89%). Although with a lower activity, MOF 2 with a redox inactive Zn(II) site, also catalyses such alcohol oxidation, which is explained by DFT calculations according to a mechanism of a similar type to that followed by the peroxidative alkane oxidation. 2 is the most active one in the ambient temperature sonochemical Knoevenagel condensation of benzaldehyde and malononitrile (yields up to 94%) and in the ambient temperature Henry C-C coupling reaction of benzaldehyde with nitroethane in water (yields > 99%), showing appreciable diastereoselectivity towards the syn isomer. The recyclability of catalysts 1 and 2 was evaluated.

KW - DFT

KW - MOFs

KW - Nitroaldol

KW - Oxidation

KW - Sonochemical Knoevenagel

KW - ZN-II

KW - AQUA COMPLEXES

KW - ACID

KW - DIASTEREOSELECTIVE HENRY REACTION

KW - LIGANDS

KW - SITES

KW - AEROBIC OXIDATION

KW - PEROXIDATIVE OXIDATION

KW - COORDINATION POLYMERS

KW - HETEROGENEOUS CATALYSTS

UR - http://www.scopus.com/inward/record.url?scp=85083053991&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/8451b52e-f2d1-394e-8f01-630878aa2fc0/

U2 - 10.1016/j.jcat.2020.03.035

DO - 10.1016/j.jcat.2020.03.035

M3 - Article

AN - SCOPUS:85083053991

VL - 385

SP - 324

EP - 337

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -