Silica-surface reorganization during organotin grafting evidenced by 119Sn DNP SENS: a tandem reaction of gem-silanols and strained siloxane bridges

被引：36

作者：

Conley, Matthew P. ^{[1
]}

Rossini, Aaron J. ^{[2
]}

Comas-Vives, Aleix ^{[1
]}

Valla, Maxence ^{[1
]}

Casano, Gilles ^{[3
]}

Ouari, Olivier ^{[3
]}

Tordo, Paul ^{[3
]}

Lesage, Anne ^{[2
]}

Emsley, Lyndon ^{[2
]}

Coperet, Christophe ^{[1
]}

机构：

[1] ETH, Dept Chem & Appl Biosci, CH-8093 Zurich, Switzerland

[2] Univ Lyon, Ctr RMN & Tres Hauts Champs, Inst Sci Analyt, CNRS,ENS Lyon,UCB Lyon 1, F-69100 Villeurbanne, France

[3] Aix Marseille Univ, CNRS, ICR UMR 7273, Fac St Jerome Case 521, F-13397 Marseille 20, France

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2014年 / 16卷 / 33期

基金：

瑞士国家科学基金会;

关键词：

DYNAMIC NUCLEAR-POLARIZATION; ORGANOMETALLIC CHEMISTRY; ROTATIONAL-ECHO; NMR-SPECTROSCOPY; TIN; COMPLEXES; RESONANCE; OXIDE; MECHANISM; MOSSBAUER;

D O I：

10.1039/c4cp01973c

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Grafting reactive molecular complexes on dehydroxylated amorphous silica is a strategy to develop "single-site" heterogeneous catalysts. In general, only the reactivity of isolated silanols is invoked for silica dehydroxylated at 700 degrees C ([SiO2-700]), though ca. 10% of the surface silanols are in fact geminal Q(2)-silanols. Here we report the reaction of allyltributylstannane with (SiO2-700] and find that the geminal Q(2)-silanols react to form products that would formally arise from vicinal Q(3)-silanols that are not present on (SiO2-700], indicating that a surface rearrangement occurs. The reorganization of the silica surface is unique to silica dehydroxylated at 700 degrees C or above. The findings were identified using Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) combined with DFT calculations.

引用

页码：17822 / 17827

页数：6

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