Copper Complexes with (2,7‐Di‐tert‐butylfluoren‐9‐ylidene)methanedithiolate: Oxidatively Promoted Dithioate Condensation

Abstract

The reaction of [Cu(NCMe) 4 ]PF 6 with piperidinium 2,7-ditert-butyl-9H-fluorene-9-carbodithioate (pipH)[S 2 C(tBuHfy)] (1; tBu-Hfy = 2,7-di-tert-butylfluoren-9-yl), affords [Cu n {S 2 C(tBu-Hfy)} n ] (2), which reacts with various P ligands to give [Cu{S 2 C(tBu-

Bridging vs. Chelating Coordination Modes of Vinylsilanes in CuI π‐Complexes: Structure and Stability

“…We believe that this unexpected result can be explained, in the first place, by a positive inductive effect of the silicon atom and its π ‐ acceptor properties, and secondly, by steric constraints of the Y, C=C‐chelating ligands, although it is generally difficult to separate these factors. It is interesting to note also that the shortening of the Cu–C α distance has been as well observed in the complexes containing five‐membered chelate rings with another soft bases such as sulfur atom21 or N–N group of pyrazole ring 22. In addition, the crystal structures with silicon containing chelates share one common feature: the silicon atom is always located at the opposite side from the axial ligand (L ax ), as though moving to occupy an additional coordination site on the copper(I) atom.…”

Copper‐Iodide‐ and Diorganyl‐Diselenide‐Promoted Cyclization of 2‐Alkynylphenols: Alternative Approach to 3‐Organoselanylbenzo[b]furans

“…Regarding the mechanisms involved in the cyclization process, we are not able to put forward a definitive proposal. Based on previous reports, and bearing in mind the fact that a stoichiometric amount of the copper salt seems to be necessary (Table , entries 11 and 12), we carried out some experiments to try to make the cyclization pathway as clear as possible, aiming to obtain relevant data that could support a plausible mechanism (Scheme ). First, substrate 1a was submitted to the cyclization conditions in the absence of a diorganyl dichalcogenide 2 [Scheme , equation (1)].…”

Cyclopentadienylidene‐ and Fluoren‐9‐ylidene‐methane‐1,1‐dithiolato Metalates of Tin, Indium and Bismuth

“…At the same time, Pianka and coworkers established a synthesis of a dithiolate derived from fluorene, Na 2 [FluoCS 2 ] [17] . Vicente and coworkers considered [FluoCS 2 ] 2− as ligand for coordination of group 10 to 11 metals and for luminescence studies [8,20–24] . As consequence of the conjugated Fluo system, the ligand shows a stronger S ‐donor character towards the central metal atom compared to other thiolates, e. g. 1,1‐ethylendithiolates.…”