Paramagnetic dithiolene complexes as metallo-ligands: ether/thioether coordination.

Dithiolene complexes as metallo-ligands: a crown-ether approach

Diolefins with an ether/thioether functionality as ligands in the coordination sphere of Ni and Rh.

A diolefin ether, trop2O (2), and a diolefin thioether, trop2S (3), have been investigated as ligand analogues of the well-established diolefin amine, trop2NH (1). Compounds 2 and 3 form different conformers in solution and in the solid state. Whereas 2 could be coordinated to Ni(0), 3 was found to be more suited for coordination to Rh(I). The coordination chemistry, electrochemical properties,...

Dehydrogenative Route to Metallo Dithiolenes: The Reaction of Zinc Polysulfides and Alkenes

Complexes of the type ZnS6(TMEDA), ZnS4(PMDETA), and ZnS4(Me3TACN) react with electrophilic alkenes to give dithiolene complexes ZnS2C2R2(amine)n. The Me3TACN complex is the most reactive, while the more conveniently prepared PMDETA complex also undergoes this reaction at useful rates. The following alkenes were successfully tested: C2H2(CO2Me)2 (cis and trans isomers), C2H3(CO2Me), C2H3(CN), 1...

Tuning of the Copper–Thioether Bond in Tetradentate N3S(thioether) Ligands; O–O Bond Reductive Cleavage via a [CuII2(μ-1,2-peroxo)]2+/[CuIII2(μ-oxo)2]2+ Equilibrium

Current interest in copper/dioxygen reactivity includes the influence of thioether sulfur ligation, as it concerns the formation, structures, and properties of derived copper-dioxygen complexes. Here, we report on the chemistry of {L-Cu}2-(O2) species L = ESE, ESP, and ESDP, which are N3S(thioether)-based ligands varied in the nature of a substituent on the S atom, along with a related N3O(ethe...

Acetylenedithiolate: alkyne complex formation renders it a dithiolate chelate ligand.

The isostructural complexes [{Tp'W(CO)(2)(eta(2)-C(2)S(2))}(2)M] (M = Ni, Pd, Pt) show that the eta(2)-C,C'-alkyne complexes of acetylenedithiolate at [Tp'W(CO)(2)](+) can generally act as dithiolate chelate ligands, leading to dithiolene type complexes.