Reaction of Mercury(0) with the I₂ Adduct of Tetraphenyldithioimidodiphosphinic Acid (SPPh₂)₂NH (HL) − Crystal Structures of [Hg(HL)I₂] and HgL₂

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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

“…[2,[5][6][7] The chalcogen (sulfur and selenium) functionalized dppa derivatives were also well defined to stabilize metal complexes by the formation of chalcogen metal bonds. [8,9,10] These unique ligands are potentially capable of coordinating through the hard nitrogen and phosphorus donor atoms along with the soft chalcogen donor atom to provide the highest coordination sphere of the metal ion required for its stabilization.…”

Copper(I) Complexes with a Cu4S6‐ and CuS4‐Type Core Obtained from the Reaction of Copper(0) with HN(SPPh2)2·I2

“…The reaction of the adduct HL·I 2 with copper(0) powder under mild conditions affords complexes [Cu [14] and [Ag(HL) 2 4+ , obtained from the reaction of 1 with HI, was also established by 31 P NMR measurements. The expansion/contraction of the Cu 4 cluster may be important as regards the activation of Ace1 and Mac1 transcription factors.…”

A highly selective off–on fluorescent chemodosimeter for Hg2+ based on a anthracene–bis(phosphinesulfide) conjugate

“…By the slow concentration in air of the solution used for the 31 P NMR measurements, it was possible to separate a white thin powder that was identified by elemental analysis, IR and 31 P NMR spectroscopies, and X-ray diffraction as the neutral complex [HgL 2 ], the X-ray crystal structure of which we have already reported. 9 In this complex, the Hg 2+ ion binds, in a slightly distorted tetrahedral arrangement, two anionic ligands L via the sulfur atoms, and for this arrangement, only one 31 P NMR signal is observed in solution at d 39.7 (CH 2 Cl 2 ). The absorption and emission spectra of the solution remaining after the separation of the [HgL 2 ] complex (Fig.…”