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  1. Abstract

    Mechanochemistry through high‐speed ball milling has become an increasingly popular method for performing organic transformations. This newfound interest in high‐speed ball milling is in part driven by the benefit of performing reactions in the absence of solvent. Mechanochemical reactions are often conducted in stainless‐steel vials with stainless‐steel balls. Since stainless steel is made of several readily oxidizable metals (Fe, Cr, and Ni), reduction reactions using water as a hydrogen source were explored using a temperature‐controlled mixer mill. Mechanistic studies suggest that the reduction proceeds via a single electron transfer (SET) pathway, with iron and nickel being essential components for the reaction.

     
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  2. Free, publicly-accessible full text available November 13, 2024
  3. Free, publicly-accessible full text available September 19, 2024
  4. This work centers around the nickel complexes derived from two tetrahydrosalen-type proligands: N , N ′-bis(2-hydroxybenzyl)- o -phenylenediamine (H 2 salophan) and N , N ′-bis(2-hydroxy-3-methylbenzyl)- o -phenylenediamine (H 2 salophan_Me). The reaction of H 2 salophan with Ni(OAc) 2 ·4H 2 O generates a dinuclear complex Ni 2 (Hsalophan) 2 (OAc) 2 or Na[Ni 2 (salophan) 2 (OAc)] when NaOH is added to assist ligand deprotonation. The reaction of H 2 salophan_Me with Ni(OAc) 2 ·4H 2 O, however, yields a mononuclear complex Ni(Hsalophan_Me) 2 . Unlike the corresponding salen-type nickel complexes, these tetrahydrosalen-type complexes are paramagentic and air sensitive (in solution). Oxidation by O 2 or peroxides results in dehydrogenation of the ligand backbone to form the salen-type complexes. 
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    Free, publicly-accessible full text available August 22, 2024
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