Pretražite po imenu i prezimenu autora, mentora, urednika, prevoditelja

Napredna pretraga

Pregled bibliografske jedinice broj: 1022403

Greener cyclooctene epoxidation with molybdenum complexes derived from aminobenzohydrazone ligands


(Mo, V, W complexes and solvent-free epoxidation) Pisk, Jana; Cvijanović, Danijela; Kuzman, Dino; Rubčić, Mirta; Agustin, Dominique; Vrdoljak, Višnja
Greener cyclooctene epoxidation with molybdenum complexes derived from aminobenzohydrazone ligands // AEM2019 Abstract Book
Guildford, Engleska, 2019. str. 38-38 (predavanje, međunarodna recenzija, sažetak, znanstveni)


CROSBI ID: 1022403 Za ispravke kontaktirajte CROSBI podršku putem web obrasca

Naslov
Greener cyclooctene epoxidation with molybdenum complexes derived from aminobenzohydrazone ligands

Autori
Pisk, Jana ; Cvijanović, Danijela ; Kuzman, Dino ; Rubčić, Mirta ; Agustin, Dominique ; Vrdoljak, Višnja

Kolaboracija
Mo, V, W complexes and solvent-free epoxidation

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
AEM2019 Abstract Book / - , 2019, 38-38

Skup
Advanced Energy Materials Conference

Mjesto i datum
Guildford, Engleska, 11-13.09.2019

Vrsta sudjelovanja
Predavanje

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
molybdenum complexes, hydrazones, homogeneous catalysis, organic solvent-free

Sažetak
INTRODUCTION Epoxides are undoubtedly the very important class of industrial chemicals, used as raw materials for epoxy resins, paints, surfactants and as intermediates in organic synthesis. Catalytic olefin epoxidation usually employs oxidants in excess, presence of organic solvents or ionic liquids. The future development of epoxidation systems is focused on environmentally friendly oxidants and highly economic processes. For that reason, eco- friendlier oxidants as O2, H2O2, or tert-butyl hydroperoxide (TBHP) have a great advantage. Among various catalysts, Mo complexes have been notably useful, particularly for the cyclic olefin epoxidation under mild reaction conditions.1, 2 A series of mononuclear, [MoO2(L)(MeOH)] and [MoO2(L)(EtOH)], and dinuclear, [MoO2(L)]2 complexes synthesized by using 2- or 4aminobenzoylhydrazone ligands derived from salicylaldehyde, 3-methoxy- and 4- methoxy-2hydroxybenzaldehyde, were tested as catalysts. The hemilabile ligand-induced catalytic enhancement which was supported by density functional theory calculations. The molecular and crystal structures of mononuclear (and dinuclear complexes described in this work were determined based on single-crystal X-ray diffraction experiments. EXPERIMENTAL STUDY The catalytic activity of Mo complexes was investigated in the cyclooctene epoxidation with aqueous TBHP, without any addition of organic solvent, following and respecting eco- friendly conditions. Complexes were tested as catalysts in order to define the impact of the: (i) coordinated ligands, (ii) architecture of the complex (mononuclear vs. dinuclear ones), (iii) catalyst loading (0.05-0.005 mmol) and (iv) reaction temperature. RESULTS AND DISCUSSION This study demonstrates the use of 2- or 4-aminoaroylhydrazone linking units for the formation of discrete Mo(VI) complexes. In these complexes, the cisMoO22+ core is coordinated to the bideprotonated ligand via the phenolate-oxygen, azomethine-nitrogen, and hydrazidato-oxygen. The sixth coordination site is occupied either by the nitrogen atom of the bridging aminobenzoylhydrazone moiety of the neighboring complex or by the oxygen atom from the coordinated alcohol molecules. Mo complexes with 2-aminobenzoylhydrazone ligands are much better catalysts than those containing 4aminobenzoylhydrazone in terms of activity and selectivity towards epoxide under proposed greener conditions. The position of the amino group on the phenyl ring strongly influences the catalytic behavior, suggesting that 2- aminobenzoylhydrazone derived complexes transform more easily to the pentacoordinated active species, crucial for the catalytic cycle. CONCLUSION The rational design of Mo(VI) catalysts with hemilabile aroylhydrazone ligands induced interesting catalytic results in terms of selectivity and conversion enhancement. The obtained catalytic results reveal that molybdenum complexes with this type of ONO hydrazones are efficient catalysts due to the peculiar noninnocent role of the NH2 substituent. Considering this is the first example of complexes with this type of ONO ligands providing excellent results operating under environmentally friendly conditions, further research will be directed in this regard.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Projekti:
HRZZ-IP-2016-06-4221 - Metalosupramolekulske strukture i anorgansko-organski polioksometalatni hibridi (MOLART) (Vrdoljak, Višnja, HRZZ - 2016-06) ( POIROT)

Ustanove:
Medicinski fakultet, Zagreb,
Prirodoslovno-matematički fakultet, Zagreb

Profili:

Avatar Url Dino Kuzman (autor)

Avatar Url Višnja Vrdoljak (autor)

Avatar Url Danijela Cvijanović (autor)

Avatar Url Jana Pisk (autor)

Avatar Url Mirta Rubčić (autor)


Citiraj ovu publikaciju

(Mo, V, W complexes and solvent-free epoxidation) Pisk, Jana; Cvijanović, Danijela; Kuzman, Dino; Rubčić, Mirta; Agustin, Dominique; Vrdoljak, Višnja
Greener cyclooctene epoxidation with molybdenum complexes derived from aminobenzohydrazone ligands // AEM2019 Abstract Book
Guildford, Engleska, 2019. str. 38-38 (predavanje, međunarodna recenzija, sažetak, znanstveni)
(Mo, V, W complexes and solvent-free epoxidation) (Mo, V, W complexes and solvent-free epoxidation) Pisk, Jana, Cvijanović, D., Kuzman, D., Rubčić, M., Agustin, D. & Vrdoljak, V. (2019) Greener cyclooctene epoxidation with molybdenum complexes derived from aminobenzohydrazone ligands. U: AEM2019 Abstract Book.
@article{article, year = {2019}, pages = {38-38}, keywords = {molybdenum complexes, hydrazones, homogeneous catalysis, organic solvent-free}, title = {Greener cyclooctene epoxidation with molybdenum complexes derived from aminobenzohydrazone ligands}, keyword = {molybdenum complexes, hydrazones, homogeneous catalysis, organic solvent-free}, publisherplace = {Guildford, Engleska} }
@article{article, year = {2019}, pages = {38-38}, keywords = {molybdenum complexes, hydrazones, homogeneous catalysis, organic solvent-free}, title = {Greener cyclooctene epoxidation with molybdenum complexes derived from aminobenzohydrazone ligands}, keyword = {molybdenum complexes, hydrazones, homogeneous catalysis, organic solvent-free}, publisherplace = {Guildford, Engleska} }




Contrast
Increase Font
Decrease Font
Dyslexic Font