Reaction of Mercury(0) with the I 2 Adduct of Tetraphenyldithioimidodiphosphinic Acid (SPPh 2 ) 2 NH (HL) − Crystal Structures of [Hg(HL)I 2 ] and HgL 2

The complex [Hg(HL)I 2 ] ( 1 ) has been synthesised by reacting liquid Hg(0) in Et 2 O under mild reaction conditions with the I 2 adduct of HL, HL·I 2 , while HgL 2 ( 2 ) has been obtained from the reaction of compound 1 with HL in CH 3 CN. A single‐crystal X‐ray investigation of 1 shows four independent molecules in the asymmetric unit, each of which contains an Hg II 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 Hg II 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 31 P 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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)