Siloxyaluminate and Siloxygallate Complexes as Models for Framework and Partially Hydrolyzed Framework Sites in Zeolites and Zeotypes

Abstract Anionic molecular models for nonhydrolyzed and partially hydrolyzed aluminum and gallium framework sites on silica, M[OSi(O t Bu) 3 ] 4 − and HOM[OSi(O t Bu) 3 ] 3 − (where M=Al or Ga), were synthesized from anionic chlorides Li{M[OSi(O t Bu) 3 ] 3 Cl} in salt metathesis reactions. Sequestration of lithium cations with [12]crown‐4 afforded charge‐separated ion pairs composed of monomeric anions M[OSi(O t Bu) 3 ] 4 − with outer‐sphere [([12]crown‐4) 2 Li] + cations, and hydroxides {HOM[OSi(O t Bu) 3 ] 3 } with pendant [([12]crown‐4)Li] + cations. These molecular models were characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy, mass spectrometry and NMR spectroscopy. Upon treatment of monomeric [([12]crown‐4)Li]{HOM[OSi(O t Bu) 3 ] 3 } complexes with benzyl alcohol, benzyloxide complexes were formed, modeling a possible pathway for the formation of active sites for Meerwin–Ponndorf–Verley (MPV) transfer hydrogenations with Al/Ga‐doped silica catalysts.