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A proton-responsive ligand becomes a dimetal linker for multisubstrate assembly via nitrate deoxygenation
Alyssa C Cabelof1, Veronica Carta1, Kenneth G Caulton1
1Department of Chemistry, Indiana University, 800 E. Kirkwood Ave., Bloomington, IN 47401, USA. caulton@indiana.edu.
Abstract:
A bidentate pyrazolylpyridine ligand (HL) was installed on divalent nickel to give [(HL)2Ni(NO3)]NO3. This compound reacts with a bis-silylated heterocycle, 1,4-bis-(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (TMS2Pz) to simultaneously reduce one of the nitrate ligands and deprotonate one of the HL ligands, giving octahedral (HL)(L-)Ni(NO3). The mononitrate species formed is then further reacted with TMS2Pz to doubly deoxygenate nitrate and form [(L-)Ni(NO)]2, dimeric via bridging pyrazolate with bent nitrosyl ligands, representing a two-electron reduction of coordinated nitrate. Independent synthesis of a dimeric species [(L-)Ni(Br)]2 is reported and effectively assembles two metals with better atom economy.
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