Cu[Al(OR^F)₄] Starting Materials and their Application in the Preparation of [Cu(S_n)]⁺(n=12, 8) Complexes

Abstract

An effective route to stable, almost-"naked" Cu(I) salts of weakly coordinating anions (WCAs) of the type [Al(OR(F))4]- has been developed. Born-Fajans-Haber cycles and theoretical calculations suggest that this methodology is useful for the generation of Cu(I) salts regardless of the larger WCA used. The first homoleptic Cu(I)-arene complex [Cu(1,2-F2C6H4)2](+)[Al{OC(CF3)3}4]- (1), the first Cu(I)-methylenechloride complex [Cu(CH2Cl2)Al{OC(CH3)(CF3)2}4] (2), and the donor-free dimer [CuAl{OCH(CF3)2}4]2 (3) were synthesized in quantitative yields by sonicating Li[Al(OR(F))4] (R(F)=C(CF3)3, C(CH3)(CF3)2, or CH(CF3)2), AgF, and a three-fold excess of CuI in 1,2-F2C6H4 (1) or CH2Cl2 (2, 3). Substances 1-3 are good starting materials for further Cu(I) chemistry, and the reaction of 1-3 with the weak Lewis base cyclooctasulfur gave the first Cu(I)-sulfur complexes of type [Cu(S12)(S8)](+)[Al{OC(CF3)3}4]- (4), [Cu(CH2Cl2)(S12)](+)[Al{OC(CF3)3}4]- (5), [A1Cu(1,5-eta1,eta1-S8)CuA1] (6; A1=[Al{OC(CH3)(CF3)2}4]-), and a Cu(I)-S8 1D coordination polymer with [Cu2(S8)2A(2)(2)] (7; A2=[Al{OCH(CF3)2}4]-), as a monomeric repeat unit. Complexes 4 and 5 are the first example of any metal coordinated to cyclo-S12 and 4 is the first example of a complex having an element in two allotropic modifications as a ligand.

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

“…Heterobimetallic Ba II À Cu I , [4] Ba II À Cu II , [5] and Al III À Cu I [6] complexes with partially fluorinated alkoxides and hetero- [7] and homometallic [8] Cu II complexes with partially fluorinated and nonfluorinated alkoxides have also been previously synthesized. Although numerous syntheses exist for Cu I alkoxide complexes, prior to this report there had been only one report of their reactivity with O 2 , in which non-fluorinated alkoxide {Cu(OR)} n species reacted with O 2 to give ligand-derived aldehydes or ketones in low yields.…”

Das Redox‐ und Koordinationsverhalten des Hexaphosphabenzol‐Liganden in [(Cp*Mo)2(μ,η6:η6‐P6)] gegenüber den “nackten” Kationen Cu+, Ag+ und Tl+

“…[20][21][22] [24] Das magnetische Moment von 3a (m eff = 1.67 m B )w urde mittels der Evans-NMR-Methode bestimmt und stimmt mit einem ungepaarten Elektron überein. [24] Im ESI-Massenspektrum wird [1] + detektiert.…”

In‐Between Complex and Cluster: A 14‐Vertex Cage in [Ag2Se12]2+

“…[1] For Se, the stability of the allotropes increases from Se 7 < Se 6 < Se 8 < Se 1 . Although being structurally related to crown ethers, only a few examples of chalcogen rings coordinated to a metal ion exist, including [Ag n (Se 6 )] n+ (n = 1, 2), [2,3] [M(S 8 ) n ] + (M = Cu; [4] Ag [5] ), [Cu(S 12 )] + , [Cu(S 8 )-(S 12 )] + . [6] All of these cations are partnered with weakly coordinating anions (WCA).…”

“…The AgAg distances of 297.10(1) (1) and 285.7(2) pm (2), respectively, are indicative for an argentophilic interaction (AE(van der Waals (vdW) radii Ag): 344 pm). [14,19] In 1, each silver atom is coordinated by one (Al-)fluorine with a Ag-F distance of 241.98 (2) 4 ] 2 (263.2 pm). This change may be attributed to stronger intracationic bonds in the noncoordinated cation, which leads to an overall contraction.…”