Copper(I) Arenethiolates with Intramolecular Coordination and the Formation of Mixed Organo(arenethiolato)copper(I) Aggregates. X-ray Structures of Trimeric [Cu(SC6H4NMe2-2)]3, Nonameric [Cu(S-1-C10H6NMe2-8)]9, and Hexanuclear [Cu3(S-1-C10H6NMe2-8)2(C⋮CtBu)]2

Two new copper(I) arenethiolates with ortho-chelating nitrogen donor atoms [Cu(SC6H4NMe2-2)]3 (5) and [Cu(S-1-C10H6NMe2-8)]9 (6) have been synthesized by reacting Me3SiSAr (Ar = C6H4NMe2-2 or 1-C10H6NMe2-8) with copper(I) chloride in a 1:1 molar ratio. Copper(I) arenethiolate 5 is a white to pale yellow solid and is trimeric in the solid state as well as in solution. Crystals of [Cu(SC6H4NMe2-2)]3 (5), C24H30Cu3N3S3, are trigonal, space group R3, with a = b = 18.2325(7) Å, c = 6.8410(4) Å, V = 1969.4(2) Å3, Z = 3, and final R = 0.028 for 1010 reflections with I ≥ 2.5σ(I) and 107 variables. Copper(I) arenethiolate 6 forms dark red crystals and is nonameric in the solid state as well as in solution. Crystals of {[Cu(S-1-C10H6NMe2-8)]9}2{C6H6}10.5 (6), C279H279Cu18N18S18, are triclinic, space group P1̄, with a = 16.081(2) Å, b = 26.650(4) Å, c = 32.747(6) Å, α = 67.320(13)°, β = 76.180(12)°, γ = 81.226(12)°, V = 12545(4) Å3, Z = 2, and final R = 0.118 for 28749 reflections and 1501 variables. Reaction of nonameric 6 with (3,3-dimethylbutynyl)copper results in the formation of the 2:1 mixed dimeric hexanuclear organo(arenethiolato)copper aggregate [Cu3(S-1-C10H6NMe2-8)2(C⋮CtBu)]2 (9), C60H66Cu6N4S4, which has been isolated as an air-stable orange solid which is insoluble in most common organic solvents. Crystals of 9 are monoclinic, space group P21/c, with a = 11.9839(5) Å, b = 12.9391(8) Å, c = 18.9482(7) Å, β = 108.326(3)°, V = 2789.1(2) Å3, Z = 2, and final R = 0.0314 for 5110 reflections with I ≥ 2.5σ(I) and 358 variables. Reaction of 6 with mesitylcopper, [Cu5(C6H2Me3-2,4,6)5], results in the formation of the 1:1 mixed organo(arenethiolato)copper aggregate [Cu2(S-1-C10H6NMe2-8)(C6H2Me3-2,4,6)] n (10), which is a yellowish-brown, slightly air-sensitive solid that is soluble in polar and aromatic hydrocarbons. The new mixed aggregates 9 and 10 are thermodynamically and kinetically very stable, and it is found that the overall structure of mixed organo(arenethiolato)copper aggregates such as 9 is insensitive to structural changes in the arenethiolate ligand.