| Summary: | The reaction of bis(pentafluorophenyl)mercury with the ligands bis(diphenylphosphano) methane P,P’-dioxide ({Ph<sub>2</sub>P(O)}<sub>2</sub>CH<sub>2</sub>) (<b>1</b>), bis{2-(N,N,N’N’-tetraethyldiaminophosphano) imidazol-1-yl} methane P,P’-dioxide ({2-PO(NEt<sub>2</sub>)<sub>2</sub>C<sub>3</sub>N<sub>2</sub>H<sub>2</sub>}<sub>2</sub>CH<sub>2</sub>) (<b>2</b>) and bis (2-diphenylphosphanophenyl) ether P,P’-dioxide ({2-PPh<sub>2</sub>(O)C<sub>6</sub>H<sub>4</sub>}<sub>2</sub>O) (<b>3</b>) afforded crystalline σ-donor complexes [{Hg(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>}<sub>2</sub>{Ph<sub>2</sub>P(O)}<sub>2</sub>CH<sub>2</sub>] (<b>1Hg</b>), [Hg(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>{2-PO(NEt<sub>2</sub>)<sub>2</sub>C<sub>3</sub>N<sub>2</sub>H<sub>2</sub>}<sub>2</sub>CH<sub>2</sub>]<sub>n</sub> (<b>2Hg</b>) and [Hg(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>{2-PPh<sub>2</sub>(O)C<sub>6</sub>H<sub>4</sub>}<sub>2</sub>O] (<b>3Hg</b>), respectively. The molecular structures of <b>1Hg</b>, <b>2Hg</b> and <b>3Hg</b> show considerable differences. In complex <b>1Hg</b>, a single bridging bidentate ligand connects two three-coordinate T-shape mercury atoms with a near linear C-Hg-C atom array. Complex <b>2Hg</b> is a one-dimensional coordination polymer in which adjacent four-coordinate mercury atoms with a linear C-Hg-C atom array are linked by bridging bidentate O,O’- ligands, whilst in complex <b>3Hg</b> a T-shape three-coordinate mercury atom is ligated by (<b>3</b>) in a monodentate fashion. The Hg-O bond lengths of complexes <b>1Hg</b>, <b>2Hg</b> and <b>3Hg</b> differ substantially (range 2.5373(14)-2.966(3) Å) owing to structural and bonding differences.
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