Synthesis and structural features of the first thallium(i) selenoether derivatives

Abstract

The first evidence for thallium(I) complexes involving selenoether ligands is presented, together with the structure determinations for the 1D chain species [T1[MeSe(CH2)3SeMe]]PF6 and the 3D network species [T1[MeSe(CH2)2SeMe]]PF6.

Thallium(i) complexes of dichalcogenido imidodiphosphinates {Tl[(EPiPr2)2N]}n (E = Te, Se, S): Synthesis, NMR spectra and a structural comparison

“…The non-chelated distances can be compared with the Tl-Se distances of 3.2769(8)-3.5058(8) A ˚in the selenoether complexes {Tl[MeSe(CH 2 ) n SeMe]}[PF 6 ] (n = 2, 3), which form coordination polymers featuring thallium centres that are ligated by selenium and fluorine donors. 23 The sulfur analogue {Tl[(SP i Pr 2 ) 2 N]} n (3c) was crystallised from CD 2 Cl 2 and a crystal structure was obtained. A thermal ellipsoid plot is displayed in Fig.…”

“…By contrast, the sulfur analogue forms a ladder structure involving vertexsharing four-membered Tl 2 S 2 rings, much like the potassium complex {K[(SPPh 2 ) 2 N]} n which forms K 2 S 2 rings joined in a similar fashion. 23 These structures vary markedly from those of the copper(I) complexes {Cu[(EP i Pr 2 ) 2 N] 3 (E = Te, 11 Se, 3 S 29 ), which are trimeric in nature. Attempts to generate a monomeric molecular species via coordination of two-electron donor ligands to the Tl I centres of 3a were unsuccessful, however NMR spectra indicate that the polymeric structures of {Tl[(EP i Pr 2 ) 2 N]} n (E = Te, Se, S) are perturbed in solution.…”

Halide Addition/Abstraction in Phosphido Derivatives: Isolation of the Thallium and Silver Intermediates

“…[17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] A noteworthy feature of this structure is the presence of o-F · · · Tl contacts, with distances Tl-F (15) ) 2.951(7) Å and Tl-F(20) ) 3.014(7) Å, which are in the range found in platinum(II) complexes containing Pt-Tl bonds, 19,22,23,27 or thallium complexes containing intra- [37][38][39][40] or intermolecular F · · · Tl contacts. 26,29,37,[41][42][43][44][45] These o-F · · · Tl contacts are also detected in solution in the 19 F NMR spectra of 5 (below).…”

The chemistry of the p-block elements with thioether, selenoether and telluroether ligands

“…Their structures are complicated, and although very different in detail, they both revealed polymeric assemblies with several long range Tl ◊ ◊ ◊ Se and Tl ◊ ◊ ◊ F interactions. 33 The structure of [Tl{MeSe(CH 2 ) 2 SeMe}]PF 6 showed each Tl(I) centre coordinated to four Se atoms from different diselenoethers, giving a distorted tetrahedral geometry (Tl-Se = 3.2769(8)-3.5058(8) A ˚). Unusually, each Se atom used its second lone pair to coordinate to an adjacent Tl centre, forming a 3D network containing Tl 2 Se 2 rhomboids (Fig.…”

“…anions occupied the channels within the cationic framework, providing a further five weak Tl ◊ ◊ ◊ F contacts per Tl centre, from three anions (Tl ◊ ◊ ◊ F 2.993(5)-3.302(5) A ˚). 33 The structure of the related complex [Tl{MeSe(CH 2 ) 3 SeMe}]PF 6 was distinctly different; the Tl(I) was coordinated linearly to two Se atoms from different ligands, Tl-Se 3.390(1) A ˚. The second Se atom on each ligand was also coordinated to an adjacent Tl(I) forming an infinite chain (Fig.…”