Structural Studies of Lithium Telluro‐ and Seleno‐Phosphorus Compounds

Abstract

Lithium tellurophosphinite [Ph2PTe][Li(TMEDA)1.33(THF)1.33] (4), ditellurophosphinate, [Ph2PTe2][Li(THF)3.5(TMEDA)0.25] (5), and selenotellurophosphinate [Ph2P(Se)Te][Li(THF)2(TMEDA)] (6) complexes have been prepared from the insertion/oxidation reactions of lithiated secondary phosphanes with elemental chalcogens and characterised by X‐ray crystallography. Compounds 4−6 contain no tellurium−lithium bonding interactions in the solid state, instead existing as ion‐separated species with THF/TMEDA‐solvated lithium cations. Reaction of dilithiated primary phosphanes with more than three equivalents of elemental selenium gives [{(c‐C6H11)P(Se)(SeLi)}2·2TMEDA] (7) via a phosphorus‐phosphorus coupling reaction. Solid state characterisation of 7 reveals the organo groups in the tetradentate tetraselenohypodisphosphinate ligand to be in an anti conformation to one another and each lithium atom to be coordinated by two selenium atoms, one from each of the diselenophosphinate groups. Multinuclear NMR spectroscopic data are consistent with retention of the solid‐state structures of 4−7 in solution. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Homoleptic Pnictogen–Chalcogen Coordination Complexes

“…), similar to those found in the few other known Ch-P coordination complexes, and are significantly longer than the Ch-P bonds observed in phosphine-chalcogenides (formal bond order = 2; Se -P: 2.07-2.11 Å; Te -P: 2.36-2.38 Å) 47 and dichalcogenophosphinates (formal bond order = 1.5; Se -P: 2.14-2.18 Å; Te -P: 2.38-2.40 Å). 48 This is consistent with a dative bonding description, where 10Ch are best described as sequestered [Ch] 2+ dications or a Ch -P single bond description where the formal positive charges lie on the phosphorus centers. The structure of 11Te is similar to the dppe derivative, crystallizing in the same space group with slightly larger unit cell parameters.…”

Alkali Metal Tetraselenohypodiphosphonates: Synthesis, NMR Spectroscopy and Crystal Structures

“…However, organophosphorus anions with selenium and tellurium are less well documented. Only a few anions including RPSe 3 2-, [6][7][8] R 2 PSe 2 -, [5,7] R 2 PTe 2 -, [9,10] R 2 PSe -, [7] R 2 PTe -, [10] R 2 PSeTe - [10] and (RP) 2 Se 6 2- [11] have been reported in the literature.…”

The Anhydride Route to Group 15/16 Ligands in Oligomeric and Polymeric Environments: From Metal Complexes to Supraionic Chemistry

“…Along this line of research, the reaction of NaSetBu and W.R. resulted in the formation of [PhSe 2 P À PSe 2 Ph] 2À , which is known for some time (Scheme 6, 10). [41] Although the reaction mechanism leading to the formation of 10 has not been investigated in detail, it seems likely that mixtures of W.R. and NaSetBu initially form sodium complexes of [PhPA C H T U N G T R E N N U N G (SetBu)Se 2 ] À anions that decompose into (tBuSe) 2 and the [PhSe 2 P À PSe 2 Ph] 2À anion observed in 10.…”