Copper (Ⅰ) 1,1-dithiolate cluster transformations . Synthesis of [Bu_4N]_6(S, i-MNT)_6], i-MNT=S_2CC(CN)_2]~-, from [Bu_4N]_4[Cu_8(i-MNT)_6] with sulfur. Reaction of the cyclic hexanuclear complex with phosphine to give the tetrahedral [Bu_4N]_4[Cu_

摘要

The novel sulfur-rich cluster anion, [Cu_6(S,i-MNT_6)~6-, 2, is obtained from the reaction of the homocubane, [Cu_8(i-MNT)_6]~4-, 1, and powdered sulfur in acetonitrile solution under basic conditions. Compound 2 crystallizes in the R bar 3 space group with a=33.519(5)A, b=33.519(5)A, c=11.748(2)A, γ=120°, and B=11431(3)A~3. The molecule contains six trigonally coordinated copper atoms linked together into a 12 membered ring by the six sulfur atoms of the bridging sulfur-rich i-MNT ligands. Six Cu~I atoms are located at the vertices of a nearly regular hexagon. The mean distance between the two planes of alternating Cu~I atoms is 0.345(2)A.