As–As Bond Formation via Reductive Elimination from a Zirconocene Bis(dimesitylarsenide) Compound

A new zirconocene bis­(arsenide) derivative, Cp₂Zr­(AsMes₂)₂ (<b>1</b>; Cp = cyclopentadienyl, Mes = 2,4,6-trimethylphenyl), has been prepared by the metathetical reaction of 2 equiv of LiAsMes₂ with Cp₂ZrCl₂ and structurally characterized. Efforts to prepare Cp₂ZrCl­(AsMes₂) (<b>2</b>) by reaction of 1 equiv of LiAsMes₂ with Cp₂ZrCl₂ yielded a mixture of products that could not be separated, including <b>1</b> and <b>2</b>, as identified by ¹H NMR spectroscopy. Compound <b>1</b> thermally decomposes with formation of As₂Mes₄, suggestive of reductive elimination to form an As–As bond. Further evidence for reductive elimination comes from effective interception of a putative zirconium­(II) intermediate with diphenylacetylene to give Cp₂Zr­(C₄Ph₄)

As–As Bond Formation via Reductive Elimination from a Zirconocene Bis(dimesitylarsenide) Compound

A new zirconocene bis­(arsenide) derivative, Cp₂Zr­(AsMes₂)₂ (<b>1</b>; Cp = cyclopentadienyl, Mes = 2,4,6-trimethylphenyl), has been prepared by the metathetical reaction of 2 equiv of LiAsMes₂ with Cp₂ZrCl₂ and structurally characterized. Efforts to prepare Cp₂ZrCl­(AsMes₂) (<b>2</b>) by reaction of 1 equiv of LiAsMes₂ with Cp₂ZrCl₂ yielded a mixture of products that could not be separated, including <b>1</b> and <b>2</b>, as identified by ¹H NMR spectroscopy. Compound <b>1</b> thermally decomposes with formation of As₂Mes₄, suggestive of reductive elimination to form an As–As bond. Further evidence for reductive elimination comes from effective interception of a putative zirconium­(II) intermediate with diphenylacetylene to give Cp₂Zr­(C₄Ph₄)

As–As Bond Formation via Reductive Elimination from a Zirconocene Bis(dimesitylarsenide) Compound

A new zirconocene bis­(arsenide) derivative, Cp₂Zr­(AsMes₂)₂ (<b>1</b>; Cp = cyclopentadienyl, Mes = 2,4,6-trimethylphenyl), has been prepared by the metathetical reaction of 2 equiv of LiAsMes₂ with Cp₂ZrCl₂ and structurally characterized. Efforts to prepare Cp₂ZrCl­(AsMes₂) (<b>2</b>) by reaction of 1 equiv of LiAsMes₂ with Cp₂ZrCl₂ yielded a mixture of products that could not be separated, including <b>1</b> and <b>2</b>, as identified by ¹H NMR spectroscopy. Compound <b>1</b> thermally decomposes with formation of As₂Mes₄, suggestive of reductive elimination to form an As–As bond. Further evidence for reductive elimination comes from effective interception of a putative zirconium­(II) intermediate with diphenylacetylene to give Cp₂Zr­(C₄Ph₄)