Preparation of a range of copper complexes of diphenylsulfimide: X-ray crystal structures of [Cu(Ph2SNH)(4)]Cl-2 and [Cu-4(mu(4)-O)(mu-Cl)(6)(Ph2SNH)(4)]

Reaction of Ph2SNH 1 with CuCl2 (molar ratio 2:1) in acetonitrile gives tra ns-[CuCl2(Ph2SNH)(2)] 2a which may be isolated as blue crystals (square pla nar form) by crystallisation from hot MeCN or as green needles (pseudo-tetr ahedral form) by slow evaporation of a CH2Cl2/petroleum ether solution. In contrast, [CuBr2(Ph2SNH)(2)] 2b, most efficiently prepared by reaction of [ Cu(Ph2SNH)(4)]Br-2 with CuBr2, appears to only exist in a dark green, pseud o-tetrahedral form. When 1.5 equivalents of 1 are reacted with CuX2 in air, [Cu-4(mu(4)-O)(mu-X)(6)(Ph2SNH)(4)] (X = Cl 3a or Br 3b) forms as orange c rystals. X-ray crystallography reveals 3a to have the expected tetrahedral arrangement of Cu atoms within an oxo-centered Cu4Cl6O core. Four equivalen ts of 1 react with CuX2 to give purple [Cu(Ph2SNH)(4)]X-2 (X = Cl 4a or Br 4b); the X-ray crystal structure of 4a reveals a square planar structure ex hibiting strong hydrogen bonding interactions between the ligands and the c ounterions. Even in the presence of excess 1, no more than four of the Liga nds may be added to a copper centre. (C) 1999 Elsevier Science Ltd. All rig hts reserved.