Reaction of mercury(0) with the I2 adduct of tetraphenyldithioimidodiphosphinic acid (SPPh2)2NH (HL) – Crystal structures of [Hg(HL)I2] and HgL2

ARAGONI, MARIA CARLA;ARCA, MASSIMILIANO;, Carrea MB;Demartin F;Devillanova FA;Garau A;ISAIA, FRANCESCO;LIPPOLIS, VITO;Verani G.

2004-01-01

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Abstract

The complex [Hg(HL)I2] (1) has been synthesised by reacting liquid Hg(0) in Et2O under mild reaction conditions with the I2 adduct of HL, HL·I2, while HgL2 (2) has been obtained from the reaction of compound 1 with HL in CH3CN. A single-crystal X-ray investigation of 1 shows four independent molecules in the asymmetric unit, each of which contains an HgII ion coordinated to two iodine atoms and two sulfur atoms of one bidentate neutral ligand in a distorted tetrahedral coordination geometry. Compound 2 consists of two anionic ligands coordinated to an HgII ion, which again displays a distorted tetrahedral coordination sphere. The reaction of 2 with HI (55 wt.-% in water) affords [Hg(HL)2](I)2 (3). Compounds 1, 2, and 3 have been characterised by FT-IR and 31P NMR spectroscopy. Density functional calculations suggest that compound 3 should feature a distorted tetrahedral coordination around the metal centre, with unequal Hg−S bond lengths.