Abstract
Treatment of tetracopper(I)-phosphonitocavitand [1 center dot Cu-4(mu-Cl)(4)(mu(4)-Cl)] (2) (1 = tetraphosphonitocavitand [rccc-2,8,14,20-tetrakis-(iso-butyl)-phosphonitocavitand (C44H48O8P4Ph4)]) with PhSeSiMe3 in THF at low temperature afforded a novel polyanionic cluster [pyH](6)[(CuCl)(9)(mu(3)-SePh)(5)(mu(4)-SePh)] (4) as a major product along with a new tetracopper(I)-phosphonitocavitand (3) with a centered mu(3)-Cl. Molecular structure of anionic cluster in 4 consists of six PhSe- bridging ligands containing five mu(3)-SePh and one exceptional mu(4)-SePh bridging nine copper atoms, of which eight copper atoms have trigonal coordination geometry and the other has distorted tetrahedral geometry.