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Al(ORF)3 (RF = C(CF3)3) activated silica: a well-defined weakly coordinating surface anion† † Electronic supplementary information (ESI) available. See DOI: 10.1039/c9sc05904k

ABSTRACT: Weakly Coordinating Anions (WCAs) containing electron deficient delocalized anionic fragments that are reasonably inert allow for the isolation of strong electrophiles. Perfluorinated borates, perfluorinated aluminum alkoxides, and halogenated carborane anions are a few families of WCAs that are commonly used in synthesis. Application of similar design strategies to oxide surfaces is challenging. This paper describes the reaction of Al(ORF)3*PhF (RF = C(CF3)3) with silica partially dehydroxylated at 700 °C (SiO2-700) to form the bridging silanol

SUBMITTER: Culver D

PROVIDER: S-EPMC8148071 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Noncovalent Interactions in Halogenated Pyridinium Salts of the Weakly Coordinating Anion [Al(OTeF5 )4 ].

Project description:The synthesis and the first structural characterization of the halogenated pyridinium salts [C5 F5 NH]+ , [C5 F4 ClNH]+ , [(C5 F5 N)2 H]+ , [(C5 Cl5 N)2 H]+ of the weakly coordinating anion (WCA) [Al(OTeF5 )4 ]- , showing noncovalent interactions in the solid state, are presented. The salts were characterized by the multinuclear NMR and IR spectroscopy as well as X-ray diffraction. Hirshfeld surface analysis and solid state structures reveal various intermolecular anion-π and σ-hole interactions between the corresponding halogenated pyridinium cations and the anion [Al(OTeF5 )4 ]- .

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Theoretical Designs for Organoaluminum C2Al4R4 with Well-Separated Al(I) and Al(III).

Project description:It is well-known that the chemistry of aluminum is dominated by Al(III) in the +3 oxidation state. Only during the past 2 decades has the chemistry of Al(I) and Al(II) been rapidly developed. However, if Al(I) and Al(III) are combined, the inherently high reactivities of Al(I) and Al(III) mostly result in their coupling with each other or interacting with surrounding elements, which easily results in significant deactivation or quenching of the desired oxidation states, as in the case of reported mixed valent Al-compounds. In this article, we report an unprecedented type of organoaluminum system, C2Al4R4 (R = H, SiH3, Si(C6H5)3, SiiPrDis2, SiMe(SitBu3)2), whose lowest-energy structure, C2Al4R4-01, contains two Al(I) and two Al(III) atoms. The global nature and bonding motif of the parent C2Al4R4-01 (R = H) were supported by an extensive global isomeric search, CBS-QB3 energy calculations, adaptive natural density partitioning, and bond order analysis. Interestingly and in sharp contrast to most organoaluminum species, C2Al4R4-01 is associated with little multicenter bonding. C2Al4R4-01 has a high feasibility of being observed either in the gas or condensed phases (with suitable substitutents). With well-separated Al(I) and Al(III), C2Al4R4-01 (with suitable substitutents) could serve as the first Al/Al frustrated Lewis pair.

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The Influence of Weakly Coordinating Cations on the O-H⋅⋅⋅O- Hydrogen Bond of Silanol-Silanolate Anions.

Project description:The reaction of a saline phosphazenium hydroxide hydrate with siloxanes led to a novel kind of silanol-silanolate anions. The weakly coordinating behavior of the cation renders the formation of silanol-silanolate hydrogen bonds possible, which otherwise suffer from detrimental silanolate-oxygen cation interactions. We investigated the influence of various weakly coordinating cations on silanol-silanolate motifs, particularly with regard to different cation sizes. While large cations favor the formation of intramolecular hydrogen bonds resulting in cyclic structures, the less bulky tetramethyl ammonium cation encourages the formation of polyanionic silanol-silanolate chains in the solid state.

| S-EPMC7839788 | biostudies-literature

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Project description:A sustainable transformation of white phosphorus (P4) into chemicals of higher value is one of the key aspects in modern phosphorus research. Even though the chemistry of P4 has been investigated for many decades, its chemical reactivity towards the simplest electrophile, the proton, is still virtually unknown. Based on quantum-chemical predictions, we report for the first time the successful protonation of P4 by the Brønsted acid H[Al(OTeF5)4](solv). Our spectroscopic results are in agreement with acid-mediated activation of P4 under protonation of an edge of the P4-tetrahedron and formation of a three-center two-electron P-H-P bond. These investigations are of fundamental interest as they permit the activation of P4 with the simplest electrophile as a new prototype reaction for this molecule.

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