Premium
Hydrophobic/Hydrophilic Interplay in 1,2,4‐Triazole‐ or Carboxylate‐Based Molybdenum(VI) Oxide Hybrids: A Step Toward Development of Reaction‐Induced Self‐Separating Catalysts
Author(s) -
Lysenko Andrey B.,
Senchyk Ganna A.,
Domasevitch Kostiantyn V.,
Neves Patrícia,
Valente Anabela A.,
Pillinger Martyn,
Gonçalves Isabel S.
Publication year - 2021
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202100389
Subject(s) - catalysis , chemistry , carboxylate , molybdenum , bridging ligand , zwitterion , ligand (biochemistry) , polyoxometalate , oxide , polymer chemistry , olefin fiber , stereochemistry , medicinal chemistry , crystallography , inorganic chemistry , organic chemistry , crystal structure , molecule , biochemistry , receptor
2‐(4H‐1,2,4‐triazol‐4‐yl)acetic acid ( trglyH ) and ( dl )‐4‐methyl‐2‐(4H‐1,2,4‐triazol‐4‐yl)pentanoic acid ( trleuH ) were used as ligands for the development of MoO 3 coordination hybrids for catalytic applications. Coordination polymers [Mo 2 O 6 ( Htrgly )] ⋅ H 2 O ( 1 ) and [MoO 3 ( trleuH )] ⋅ 0.5H 2 O ( 2 ) were prepared and structurally characterized. Compound 1 adopts a structure in which edge‐sharing MoO 6 octahedra are organized in a ribbon motif via μ 3 ‐O bridges. The Htrgly ligand exists as a zwitterion: −CO 2 − links two Mo VI in a μ 2 ‐η 1 : η 1 mode, while positively charged triazolium is left uncoordinated. In 2 , Mo atoms are joined in a chain through μ 2 ‐O. The more hydrophobic trleuH appears in a nonionized form and its [N−N] sites serve as a “clamp” for supporting the [−OMo(O) 2 −OMo(O) 2 ( tr ) 2 ] n sequence. The complexes were explored for liquid phase catalytic epoxidation of cis ‐cyclooctene, using H 2 O 2 or tert ‐butylhydroperoxide as oxidants. The hybrids showed good catalytic activity, and 2 behaved as a reaction‐induced self‐separating catalyst for olefin epoxidation with H 2 O 2 , presenting advantages of homogeneous and heterogeneous catalysis.