Abstract
AbstractSeveral thiolate‐bridged dichromium complexes with Cp* (Cp*=η5‐C5Me5) as auxiliary ligands were designed and synthesized through the salt metathesis, which all contain two six‐coordinate chromium centers in the formal valence of +3. These complexes are all paramagnetic species, which are in good agreement with the experimental results that broad and paramagnetically shifted proton resonances appear in the 1H NMR spectra. Furthermore, variable‐temperature solid‐state magnetic susceptibility studies reveal the two chromium centers of these complexes are both in an S=3/2 high‐spin state with a strong antiferromagnetic coupling. Simulated values of antiferromagnetic coupling constant for these complexes are directly related to the distances of the two CrIII centers confirmed by X‐ray crystallography. In addition, in the presence of dehalogenation agent AgPF6, complexes [Cp*CrCl(μ‐SR)2CrClCp*] (3, R=Et; 4, R=iPr) and [Cp*Cr(μ‐Cl)(μ‐SEt)2CrCp*][BPh4] (5) containing easily removable chloride can achieve the catalytic oxidation of organic substrates, such as PPh3, 1,4‐cyclohexadiene and 1,2‐diphenylhydrazine under an oxygen atmosphere.
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