Immobilization of thallium by tandem oxidation/reduction-complexation of thallium(I/III)

“Crowned” Univalent Indium Complexes as Donors? Experimental and Computational Insights on the Valence Isomers of EE′X4 Species

“…For example, instead of the simple formation of an InÀIn bond followed by, or preceded by, OTf-forhalide exchange (as illustrated by routes A and B in Scheme 1), it is plausible that the triflate anion may first be abstracted by the InX 3 Lewis acid to generate a salt of the form [In( [18] ; although the thallium analogues of these salts have been characterized, [44][45][46][47][48] such mixed-valent indium salts had been posited to exist by Taylor and Tuck as early as 1981 but conclusive evidence of their existence has never been produced. [49] The formal insertion of the In I center into an In À X bond of the tetrahaloindate anion (route C in Scheme 1) which, because of geometrical considerations, most likely occurs by the [50] in toluene, as outlined in Scheme 2.…”

Structural and selectivity of 18-crown-6 ligand in lanthanide–picrate complexes

“…doi:10.1016/j.jorganchem.2008.04.046 molecular structure has been reported in alkaline-18C6 complexes [24][25][26][27]. The structure of the [alkaline-18C6] + fragment with the largest size metal ion is relatively rigid and exists as a halfsandwich encapsulate [24,27], with the small metal ion situated out of the crown ligand plane [27][28][29][30]. This distortion results from a mismatch between the metal ion and the crown ether cavity sizes [26,27], a demand for the most efficient interaction of the metal ion with the counter anion, a demand for dense packing of the structural component [24] and the dissymmetry of the environment of the inner coordination sphere from the two axial sides [4].…”

Electrophilic activation and the formation of an unusual Tl+/Cr3+ tetranuclear ion-complex adduct

“…However, coordination of a Tl + cation to a metal-bound halide has been reported in some cases. [7][8][9][10][11][12][13][14][15][16][17][18] We recently found that the reaction of the Pt(II) complex [Pt(CH 2 Ph)Cl(PCH 2 -ox)] (PCH 2 -ox = k 2 -P,N-(oxazolinylmethyl)diphenylphosphine) with TlPF 6 selectively afforded an unexpected bimetallic complex containing a new benzylstabilized Tl-Pt bond while retaining the Pt-Cl bond. 19 In view of the considerable interest for the study of Cr-based homogeneous catalysts for ethylene oligomerization and polymerization, 20-42 triggered by the pioneering discoveries at Union Carbide 20 and Phillips Petroleum, 21 we decided to prepare Cr(III) complexes with hybrid ligands and during attempts to form a cationic complex by chloride abstraction, we unexpectedly obtained a novel Cr(III)/Tl(I) ioncomplex adduct exhibiting unusual interactions involving the Tl + cation of possible relevance to catalyst activation steps.The 1 : 1 reaction between [CrCl 3 (THF) 3 ] and bis(2picolyl)phenylphosphine (NPN) 43 afforded an air-stable, blue complex in high yield.…”