Cu[Al(ORF)(4)] Starting Materials and their Application in the Preparation of [Cu(S-n)](+) (n=12, 8) Complexes

An effective route to stable, almost-naked Cut salts of weakly coordinating anions (WCAs) of the type [Al(ORF)(4)](-) has been developed. Born-Fajans-Haber cycles and theoretical calculations suggest that this methodology is useful for the generation of Cut salts regardless of the larger WCA used. The first homoleptic Cu-1-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(ORF)(4)] (R-F = C(CF3)(3), C(CH3)(CF3)(2), or CH(CF3)(2)) AgF, and a three-fold excess of Cul 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(S-12)(S-8)](+) [Al{OC(CF3)(3)}(4)](-) (4), [Cu(CH2Cl2)-(S-12)](+)[Al{OC(CF3)(3)}(4)](-) (5). [A(I)Cu(1,5-eta(1),eta(1)-S-8)CuA(1)] (6; A(1)=[Al{OC(CH3)-(CF3)(2)}(4)](-)) and a Cu-I-S-8 1D coordination polymer with [Cu-(S-8)(2)A(2)(2)] (7; A(2) = [Al{OCH(CF3)(2)}(4)](-)), as it monomeric repeat unit. Complexes 4 and 5 are the first example of any metal coordinated to cyclo-S-12 and 4 is the first example of a complex having an element in two allotropic modifications as a ligand.