Inorganic heterocycles based on alumosilicate-sulfide ligand

García-Ríos, Jessica; Hernández-Campos, René Francisco; Rascón‐Cruz, Fernando; Huerta-Lavorie, Raúl; Martı́nez-Otero, Diego; Jancik, Vojtech

doi:10.1016/j.poly.2015.05.029

Cited by 4 publications

(4 citation statements)

References 54 publications

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“…Such stabilization was informed by us previously for related species Al L {O-AlMe(THF)}{OSi(O t Bu) 2 (μ-O)} (Scheme S2). In this case, a mixture of L H (δ = 4.89 ppm) and a new product with δ = 4.93 ppm for the proton γ was obtained (Figure S9). Importantly, the 1 H NMR spectrum of the crude product contains a singlet at δ = −0.59 ppm with an integral corresponding to one Al–Me group per 1 equiv of L , indicating that it could be IM1 ·THF.…”

Section: Results and Discussionmentioning

confidence: 93%

“…Importantly, we have observed such methyl group migration previously, making this step feasible (Scheme S2). Although the reaction was performed in hexane where it is estimated that 99.995% of AlMe 3 exists as a Me 2 Al(μ-Me) 2 AlMe 2 dimer, the presence of the silicate oxygen atoms of 1 guarantees that a significant quantity or all of AlMe 3 will be monomeric because of its coordination to the silicate moiety prior to the reaction . In an attempt to isolate IM1 or its derivative, we have performed a reaction between 1 and 0.8 equiv of AlMe 3 ; however, in the region of the γ proton of the ligand L in 1 H NMR, only the remaining 1 (δ = 4.97 ppm), the product 2 (δ = 4.87 ppm), and L H (δ = 4.89 ppm, formed by the decomposition of 1 ) were observed (Figure S6).…”

Section: Results and Discussionmentioning

confidence: 99%

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Aluminum-Triggered Condensation of Vicinal Silicate Groups into a Bicyclic Alumosilicate

et al. 2020

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The molecular alumosilicates AlL{OSi(O t Bu) 2 O}-[OSi{(μ 3 -O)(MR 2 ) 2 (μ-O t Bu)}(O t Bu)] (L = HC[CMeNAr] 2 − , where M = Al, R = Me (2), Et (3), and i Bu (4) and M = Ga, R = Me (5)) were obtained from the reaction of AlL{OSi-(O t Bu) 2 (OH)} 2 (1) with 1 or 2 equiv of the respective organometallic precursor. These compounds have a central bicyclic inorganic core formed by a six-membered AlSi 2 O 3 alumosilicate ring with a Si−O−Si unit connected via a Si−O bond to a fourmembered Al 2 O 2 alumoxane ring. These compounds are formed even though 1 is specifically designed to yield 4R alumosilicate rings that would obey the Loẅeinstein's and Dempsey's rules about concatenation between silicon and aluminum tetrahedra in alumosilicates. We propose a mechanism for this rearrangement, based on the experimental evidence and density functional theory calculations, that involves a κ 3 μ 2 coordination of a silicate unit to two AlMe 2 groups, which weakens one Si−O bond and explains how aluminum atoms can cleave Si−O bonds. Furthermore, formation of the products experimentally confirms the theory that Al−O−Al groups can exist in alumosilicates if the oxygen atom belongs to an OH moiety.

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Section: Results and Discussionmentioning

confidence: 93%

Section: Results and Discussionmentioning

confidence: 99%

Aluminum-Triggered Condensation of Vicinal Silicate Groups into a Bicyclic Alumosilicate

et al. 2020

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“…It is noteworthy, that compound 6 is the lighter homologue of the sulfur derivative LAl(m 3 -S)(AlMe 3 )(m-AlMe 2 )(m-O)Si[(m 3 -O)(AlMe 2 )]-(m-OtBu)(OtBu) reported earlier by our group. 11 The equimolar reaction of 2 with GaMe 3 resulted in the formation of [LAl(m-OH)(m-O)Si(m-O)(OtBu) 2 ]GaMe 2 (7) with 80% yield. The IR (ñ 3646 cm À1 ) and 1 H NMR spectra (d 1.53 ppm) of 7 conrm the presence of the Al(OH)Ga group.…”

Section: Resultsmentioning

confidence: 99%

“…The difference between the polar M-O and M/O bond is 0.16 A for 6 and 0.25 A for 7. As the covalent radii of both elements are 11,18 The coordination of another aluminum atom to the silicate moiety in 5 and 6, results in a signicant strain release in the Al 2 SiO 3 ring, as the Al/Al distance increases from 3.057(1) A in 4 to 3.203(1) A in 5 and 3.206(1) A in 6, but is still shorter than in 3 3.332(1) A. Consequently, the conformation of the Al 2 SiO 3 ring changes from nearly planar (4) to boat (5) or a twisted chair (6) conformation. Furthermore, the coordination of three aluminum atoms to O (10)…”

Section: X-ray Structural Analysismentioning

confidence: 99%