Grafting of [Mn(CH2tBu)2(tmeda)] on silica and comparison with its reaction with a silsesquioxane

Virginie Riollet, Elsje Alessandra Quadrelli, Christophe Copéret*, Jean Marie Basset, Richard A. Andersen, Klaus Köhler, Rolf Michael Böttcher, Eberhardt Herdtweck

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

36 Scopus citations


The reaction of [Mn-(CH2rBu)2(tmeda)] (1) and a silica partially dehydroxylated at 700°C (SiO2/700) yields a single surface species [(≡SiO)Mn(CH2tBu)(tmeda)] (2a; tmeda = tetramethylethylendiamine), while a mixture of 2a and [(≡SiO) 2Mn-(tmeda)] (2b) is obtained by using SiO2/200, SiO 2/300, or SiO2/500 as evidenced by mass balance analysis, and IR and EPR spectroscopy. The reaction of 1 and (c-C5H 9)7Si7O12SiOH (3), a soluble silanol that is a molecular model for a silica support, generates the bis-siloxy complex 4, [{(c-C5H9)7Si7O 12SiO)2Mn(tmeda)2], in a quantitative yield; compound 4 was characterized by single-crystal X-ray diffraction. These reactions exemplify the limitation of considering molecular silanol derivatives as straightforward and reliable homogeneous models for silica, and address the need for thorough characterization of surface species by the use of surface-science techniques. These studies show the possibility of preparing coordinatively and geometrically unique surface species that would be difficult to prepare by solution chemistry methods; insights into the chemical and physical properties of these surface species are also gained.

Original languageEnglish (US)
Pages (from-to)7358-7365
Number of pages8
JournalChemistry - A European Journal
Issue number24
StatePublished - Dec 9 2005
Externally publishedYes


  • Manganese
  • Silica
  • Silsesquioxane
  • Surface chemistry

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Organic Chemistry


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