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Issue 9, 1997
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Synthesis and crystal structure of the subvalent mercury cluster[triangulo-Hg3(µ-dmpm)4][O3SCF3]4(dmpm = Me2PCH2PMe2)

Abstract

The subvalent mercury cluster [triangulo-Hg 3 (µ-dmpm) 4 ][O 3 SCF 3 ] 4 [dmpm = bis(dimethylphosphino)methane], involving the +4/3 oxidation state of mercury, was formed by reaction of [Hg 2 ] 2+ with 2 equivalents of dmpm or by reduction of a mixture of [Hg(Me 2 SO) 6 ][O 3 SCF 3 ] 2 and dmpm in the molar ratio 2∶4 with elemental Hg. The cation consists of a Hg 3 triangle [Hg–Hg 276.68(14), 280.99(14) and 295.53(14) pm] in which two edges are bridged by one dmpm ligand and the third edge is doubly bridged by a pair of dmpm ligands. The three Hg atoms and the phosphorus atoms of the singly bridging dmpm ligands are nearly in a plane. The dihedral angles of the Hg 3 triangle and the mean planes formed by the doubly bridged Hg atoms and the phosphorus atoms of the two bridging dmpm ligands respectively are 61 and 46°. The complex is fluxional on the 31 P NMR time-scale at 81 MHz at ambient temperature due to intramolecular exchange between the two different types of dmpm ligands.

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Article type: Paper
DOI: 10.1039/A700483D
Citation: J. Chem. Soc., Dalton Trans., 1997, 1607-1610
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    Synthesis and crystal structure of the subvalent mercury cluster [triangulo-Hg3(µ-dmpm)4][O 3SCF3]4 (dmpm = Me2PCH2PMe2)

    A. Mühlecker-Knoepfler, E. Ellmerer-Müller, R. Konrat, K. Ongania, K. Wurst and P. Peringer, J. Chem. Soc., Dalton Trans., 1997, 1607
    DOI: 10.1039/A700483D

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