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Stable monovalent aluminum(i) in a reduced phosphomolybdate cluster as an active acid catalyst
Ya-Qi Zhang1, Lai-Yun Zhou1, Yuan-Yuan Ma1
1Hebei Key Laboratory of Organic Functional Molecules, National Demonstration Center for Experimental Chemistry Education, College of Chemistry and Material Science, Hebei Normal University Shijiazhuang Hebei 050024 People's Republic of China mayy334@hebtu.edu.cn wanglanzhi@126.com hanzg116@126.com hanzg116@hebtu.edu.cn.
Abstract:
Low-valent aluminum Al(i) chemistry has attracted extensive research interest due to its unique chemical and catalytic properties but is limited by its low stability. Herein, a hourglass phosphomolybdate cluster with a metal-center sandwiched by two benzene-like planar subunits and large steric-hindrance is used as a scaffold to stabilize low-valent Al(i) species. Two hybrid structures, (H3O)2(H2bpe)11[AlIII(H2O)2]3{[AlI(P4MoV 6O31H6)2]3·7H2O (abbr. Al6{P4Mo6}6) and (H3O)3(H2bpe)3[AlI(P4MoV 6O31H7)2]·3.5H2O (abbr. Al{P4Mo6}2) (bpe = trans-1,2-di-(4-pyridyl)-ethylene) were successfully synthesized with Al(i)-sandwiched polyoxoanionic clusters as the first inorganic-ferrocene analogues of a monovalent group 13 element with dual Lewis and Brønsted acid sites. As dual-acid catalysts, these hourglass structures efficiently catalyze a solvent-free four-component domino reaction to synthesize 1,5-benzodiazepines. This work provides a new strategy to stabilize low-valent Al(i) species using a polyoxometalate scaffold.
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