Towards Heteroleptic Dicoordinate Cu^II Complexes

Abstract

In this work we detail our efforts to systematically generate stable dicoordinate Cu II complexes. Initial experiments via metathesis reactions of a bulky potassium carbazolide (RK) with copper(II) salts indeed yielded a stable product, RCuOTf (1). However, subsequent attempts to grasp systematic synthetic access to complexes of the type RCuX (X = monoanionic ligand) proved difficult as many of the complexes rapidly decomposed in solution. By using triflate-related ligands such as ethyl sulfate and bistriflimide, the additional dicoordinate copper complexes RCuOSO 3 Et (2), [RCu(THF)][Cu(NTf 2 ) 2 ] (3) and RCuNTf 2 (4) could be isolated. Spectroscopic indications corroborate more Cu I than Cu II character in all RCuX derivatives.

Intricacies and Mechanism of p‐Doping Spiro‐MeOTAD Using Cu(TFSI)2

“…The same cuprate(I) anion [Cu I (TFSI) 2 ] – is very likely formed during our solvent and oxygen free doping environment and responsible for the high stability (low EA Cu(I)/Cu(0) ) via complexation and lower N TFSI ‐Cu bond distance of ≈1.9 Å compared to ICu bond distance of 2.62 Å in γ‐CuI. [ 55–57 ] To test the possibility for [Cu I (TFSI) 2 ] – formation, we mixed equimolar amounts of Spiro‐MeOTAD and Cu(TFSI) 2 in dichloromethane. A black, crystal‐like salt was isolated by an anti‐solvent approach (Figure S25, Supporting Information).…”

Efficient fluorescence of alkali metal carbazolides

“…28 In previous works, our group prepared the potassium carbazolide [( dtbp Cbz)K] (3a) by deprotonation of the ( dtbp Cbz)-H ligand with benzyl potassium. [29][30][31][32] It was noted that the compound is highly luminescent but at that time metathesis reactions were the focus of study. In order to gain detailed insight into the luminescence behaviour of the carbazolide entity and the influence of the coordinated group 1 element, two series of compounds were prepared: a) the unsolvated complexes [( dtbp Cbz)M], M = Li (1a), Na (2a), K (3a), Rb (4a), Cs (5a) and b) the toluene solvates [( dtbp Cbz)M(Tol) n ], M = Li (1b), Na (2b), K (3b), Rb (4b), Cs (5b).…”

Hydride Abstraction from a BH4– Anion in a Carbazolyl Lanthanum Boranate

“…Our group introduced the bis-arene-substituted carbazolyl ligand 1,8-bis(3,5-di- tert -butylphenyl)-3,6-di- tert -butyl-carbazolyl ( dtbp Cbz), which has already been applied to s-, p-, and d-block-element chemistry. − As the bulky dtbp Cbz ligand mainly acts as a classic monodentate amide σ donor that could even accommodate the large Ba 2+ cation in that position, coordination of a lanthanide ion without any coligands could be feasible as well. However, the initial attempts to generate dtbp Cbz lanthanide complexes by employing LnCl 3 as precursors were futile.…”