As–As Bond Formation
via Reductive Elimination from a Zirconocene Bis(dimesitylarsenide)
Compound
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Abstract
A new zirconocene bis(arsenide) derivative, Cp<sub>2</sub>Zr(AsMes<sub>2</sub>)<sub>2</sub> (<b>1</b>; Cp = cyclopentadienyl,
Mes = 2,4,6-trimethylphenyl), has been prepared by the metathetical
reaction of 2 equiv of LiAsMes<sub>2</sub> with Cp<sub>2</sub>ZrCl<sub>2</sub> and structurally characterized. Efforts to prepare Cp<sub>2</sub>ZrCl(AsMes<sub>2</sub>) (<b>2</b>) by reaction of 1
equiv of LiAsMes<sub>2</sub> with Cp<sub>2</sub>ZrCl<sub>2</sub> yielded
a mixture of products that could not be separated, including <b>1</b> and <b>2</b>, as identified by <sup>1</sup>H NMR spectroscopy.
Compound <b>1</b> thermally decomposes with formation of As<sub>2</sub>Mes<sub>4</sub>, 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 Cp<sub>2</sub>Zr(C<sub>4</sub>Ph<sub>4</sub>)
