Aluminium-catalysed isocyanate trimerization, enhanced by exploiting a dynamic coordination sphere

Bahili, Mohammed; Stokes, Emily C.; Amesbury, Robert C.; Ould, Darren M. C.; Christo, Bashar; Horne, Rhian J.; Kariuki, Benson M.; Stewart, Jack A.; Taylor, Rebekah L.; Williams, Peter A.; Jones, Matthew D.; Harris, Kenneth D. M.; Ward, Benjamin D.

doi:10.1039/c9cc03339d

Cited by 23 publications

(24 citation statements)

References 37 publications

(36 reference statements)

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“…Despite some positional disorder, the presence of one C–S bond was clearly apparent in the molecular structure of this compound (1.66 ± 0.01 Å). The two C–O bonds (1.22 ± 0.02 Å) were significantly shorter, and were in the range of those reported for the carbonyl bonds of 1-Me (1.21 ± 0.01 Å) [ 26 , 27 ]. The central heterocycle was nearly coplanar.…”

Section: Resultssupporting

confidence: 67%

1,3,5-Triaryl-1,3,5-Triazinane-2,4,6-Trithiones: Synthesis, Electronic Structure and Linear Optical Properties

et al. 2020

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The synthesis of four new 1,3,5-triaryl-1,3,5-triazinane-2,4,6-trithione derivatives (thioisocyanurates) and two new partially thionated analogues from the corresponding 1,3,5-triaryl-1,3,5-triazinane-2,4,6-triones (isocyanurates) is reported, together with their spectroscopic properties. DFT calculations and comparison with the corresponding isocyanurates evidence the impact of the oxygen-for-sulfur replacement on the electronic structure and linear optical properties of these heterocycles. A bathochromic shift of the absorption bands and more efficient quenching of the fluorescence was observed.

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Section: Resultssupporting

confidence: 67%

1,3,5-Triaryl-1,3,5-Triazinane-2,4,6-Trithiones: Synthesis, Electronic Structure and Linear Optical Properties

et al. 2020

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“…, 1.817(3)–1.824(4) Å, are typical of octahedrally coordinated aluminum centers. 74–76 The results of continuous-shape measure calculations showed an insignificant departure from an ideal octahedron for the coordination environment around Al1 with the S (Oh) parameter of 0.170. 77…”

Section: Resultsmentioning

confidence: 99%

Use of group 13 aryloxides for the synthesis of green chemicals and oxide materials

et al. 2022

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“…1 H NMR (400 MHz, acetone- d 6 ): δ 7.29 (t, J = 6.1 Hz, 12H), 2.36 (s, 9H) ppm; 13 C{ 1 H} NMR (100 MHz, acetone- d 6 ): δ 205.3, 129.4, 128.7, and 20.3 ppm. 65 …”

Section: Experimental Sectionmentioning

confidence: 99%

Role of Acetate Anions in the Catalytic Formation of Isocyanurates from Aromatic Isocyanates

et al. 2021

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The formation of isocyanurates via cyclotrimerization of aromatic isocyanates is widely used to enhance the physical properties of a variety of polyurethanes. The most commonly used catalysts in industries are carboxylates for which the exact catalytically active species have remained controversial. We investigated how acetate and other carboxylates react with aromatic isocyanates in a stepwise manner and identified that the carboxylates are only precatalysts in the reaction. The reaction of carboxylates with an excess of aromatic isocyanates leads to irreversible formation of corresponding deprotonated amide species that are strongly nucleophilic and basic. As a result, they are active catalysts during the nucleophilic anionic trimerization, but can also deprotonate urethane and urea species present, which in turn catalyze the isocyanurate formation. The current study also shows how quantum chemical calculations can be used to direct spectroscopic identification of reactive intermediates formed during the active catalytic cycle with predictive accuracy.

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Aluminium-catalysed isocyanate trimerization, enhanced by exploiting a dynamic coordination sphere

Abstract: The lability of aluminium is exploited to give a highly effective catalyst for the trimerization of isocyanates.

Cited by 23 publications

References 37 publications

1,3,5-Triaryl-1,3,5-Triazinane-2,4,6-Trithiones: Synthesis, Electronic Structure and Linear Optical Properties

1,3,5-Triaryl-1,3,5-Triazinane-2,4,6-Trithiones: Synthesis, Electronic Structure and Linear Optical Properties

Use of group 13 aryloxides for the synthesis of green chemicals and oxide materials

Role of Acetate Anions in the Catalytic Formation of Isocyanurates from Aromatic Isocyanates

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