Synthesis, characterization, and molecular structure of the first metal complex containing thallium chloride as a ligand. A novel carrier of thallium(I)

Syntheses and Structures of Ruthenium Complexes Containing a Ru‐H‐Tl Three‐Center–Two‐Electron Bond

“…The short Tl⋅⋅⋅H distances observed in these previously reported examples are mainly associated with 1,3‐ or 1,4‐non‐bonded contacts. We also noted that the solid state structure of [(PP 3 )RuH(η 1 ‐ClTl)]PF 6 (where PP 3 is P(CH 2 CH 2 PPh 2 ) 3 ] contains a Tl−H contact distance of 2.6 (2) Å) which is shorter than the sum of the van der Waals radii of H (1.20 Å) and Tl (2.27 Å) and was attributed to residual electrostatic interaction …”

“…First of all, they are the first structurally characterized h 2 -(HÀ EX n )c omplexes in which the main-group element Ei so f period 6. [41] Complexes 5 and 6 have been characterized by NMR spectroscopy and elemental analysis.T he structure of the trimetallic complex [{CpRu(dppm)} 2 (m-Tl)]PF 6 (5)h as also been confirmed by X-ray diffraction (see the Supporting Information for details). To the best of our knowledge,t here is no structurally characterized thallium hydride species with aterminal hydride bond.…”

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.…”

“…2+ and [( [9]aneS 3 )(PPh 3 )Ru(m-Cl) 2 Tl] 2 2+ were found to decompose in Ocoordinating solvents. 8, 9 After activation with methylaluminoxane (MAO), 1 was active for ethylene oligomerization (2900 g g(Cr) -1 •h -1 ), producing a mixture of butenes (12%; of which 99% a-butene), hexenes (22%; 88% a-hexene), octenes (17%; 87% a-octene), decenes (9%; 72% a-decene) and higher a-olefins. Similar activities and product distribution were observed for the 2/MAO system, suggesting that under these catalytic conditions, the Cr(III)/Tl(I) pseudodimer 2 may not be persistent.…”

Syntheses and Structures of Ruthenium Complexes Containing a Ru‐H‐Tl Three‐Center–Two‐Electron Bond

“…Thes hort Tl···H distances observed in these previously reported examples are mainly associated with 1,3-or 1,4-non-bonded contacts.W ealso noted that the solid state structure of [(PP 3 )RuH(h 1 -ClTl)]PF 6 (where PP 3 is P(CH 2 CH 2 PPh 2 ) 3 ]c ontains aT l À Hc ontact distance of 2.6 (2) )which is shorter than the sum of the van der Waals radii of H( 1.20 )a nd Tl (2.27 )a nd was attributed to residual electrostatic interaction. [41]…”