Issue 9, 1997

Synthesis and crystal structure of the subvalent mercury cluster [triangulo-Hg3(µ-dmpm)4][O 3SCF3]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.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1997, 1607-1610

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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