[(CH3)5C5]2Th(CH3)2/Silica Surface Chemistry. High-Resolution 13C CPMAS NMR Evidence for Alkylation of Surface Silicon Sites

Paul J. Toscano; Tobin J. Marks

doi:10.1021/la00072a029

[(CH₃)₅C₅]₂Th(CH₃)₂/Silica Surface Chemistry. High-Resolution ¹³C CPMAS NMR Evidence for Alkylation of Surface Silicon Sites

Paul J. Toscano, Tobin J. Marks

Northwestern University

Research output: Contribution to journal › Article › peer-review

47 Citations (Scopus)

Abstract

The reaction of Cp’₂Th(¹³CH₃)₂ (Cp’ = η⁵-Me₅C₅) with dehydroxylated silica (ca. 0.4 surface OH/nm²) has been studied by high-resolution ¹³C CPMAS NMR spectroscopy. On the basis of ¹³C chemical shifts, relative signal intensities, and NMR data from model compounds and model reactions, it is proposed that the predominant adsorption pathway involves methyl transfer from thorium to surface silicon sites. The products of this Si-O cleavage process are surface Si-CH₃ and Cp’₂Th(CH₃)-siloxide functionalities. The resulting thorium environment appears to be somewhat more electron rich than in the analogous surface complex on dehydroxylated γ-alumina.

Original language	English
Pages (from-to)	820-823
Number of pages	4
Journal	Langmuir
Volume	2
Issue number	6
DOIs	https://doi.org/10.1021/la00072a029
Publication status	Published - Jan 1 1986

ASJC Scopus subject areas

Materials Science(all)
Condensed Matter Physics
Surfaces and Interfaces
Spectroscopy
Electrochemistry

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title = "[(CH3)5C5]2Th(CH3)2/Silica Surface Chemistry. High-Resolution 13C CPMAS NMR Evidence for Alkylation of Surface Silicon Sites",

abstract = "The reaction of Cp{\textquoteright}2Th(13CH3)2 (Cp{\textquoteright} = η5-Me5C5) with dehydroxylated silica (ca. 0.4 surface OH/nm2) has been studied by high-resolution 13C CPMAS NMR spectroscopy. On the basis of 13C chemical shifts, relative signal intensities, and NMR data from model compounds and model reactions, it is proposed that the predominant adsorption pathway involves methyl transfer from thorium to surface silicon sites. The products of this Si-O cleavage process are surface Si-CH3 and Cp{\textquoteright}2Th(CH3)-siloxide functionalities. The resulting thorium environment appears to be somewhat more electron rich than in the analogous surface complex on dehydroxylated γ-alumina.",

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year = "1986",

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N2 - The reaction of Cp’2Th(13CH3)2 (Cp’ = η5-Me5C5) with dehydroxylated silica (ca. 0.4 surface OH/nm2) has been studied by high-resolution 13C CPMAS NMR spectroscopy. On the basis of 13C chemical shifts, relative signal intensities, and NMR data from model compounds and model reactions, it is proposed that the predominant adsorption pathway involves methyl transfer from thorium to surface silicon sites. The products of this Si-O cleavage process are surface Si-CH3 and Cp’2Th(CH3)-siloxide functionalities. The resulting thorium environment appears to be somewhat more electron rich than in the analogous surface complex on dehydroxylated γ-alumina.

AB - The reaction of Cp’2Th(13CH3)2 (Cp’ = η5-Me5C5) with dehydroxylated silica (ca. 0.4 surface OH/nm2) has been studied by high-resolution 13C CPMAS NMR spectroscopy. On the basis of 13C chemical shifts, relative signal intensities, and NMR data from model compounds and model reactions, it is proposed that the predominant adsorption pathway involves methyl transfer from thorium to surface silicon sites. The products of this Si-O cleavage process are surface Si-CH3 and Cp’2Th(CH3)-siloxide functionalities. The resulting thorium environment appears to be somewhat more electron rich than in the analogous surface complex on dehydroxylated γ-alumina.

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[(CH₃)₅C₅]₂Th(CH₃)₂/Silica Surface Chemistry. High-Resolution ¹³C CPMAS NMR Evidence for Alkylation of Surface Silicon Sites

Abstract

ASJC Scopus subject areas

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