Abstract
The reaction of [Cu(NCMe)~4~]PF~6~ with piperidinium 2,7‐di‐tert‐butyl‐9__H__‐fluorene‐9‐carbodithioate (pipH)[S~2~C(t__Bu‐Hfy)] (1; t__Bu‐Hfy = 2,7‐di‐tert‐butylfluoren‐9‐yl), affords [Cu~n~{S~2~C(t__Bu‐Hfy)}~n~__] (2), which reacts with various P ligands to give [Cu{S~2~C(__t__Bu‐Hfy)}L~2~] [L = PPh~3~ (3a), PCy~3~ (3b), P__i__Pr~3~ (3d); L~2~ = 1,1′‐bis(diphenylphosphanyl)ferrocene (dppf, 3c), bis(diphenylphosphanyl)methane (dppm, 3e)]. Compounds 3a–c react with atmospheric oxygen and moisture in the presence of NEt~3~ to give the dinuclear complexes [Cu~2~{[SC=(__t__Bu‐fy)]~2~S}L~2~] [__t__Bu‐fy = 2,7‐di‐tert‐butylfluoren‐9‐ylidene; L = PPh~3~ (4a), PCy~3~ (4b); L~2~ = dppf (4c)], which contain a new dithiolato ligand formally resulting from the condensation of two dithioato ligands with loss of a sulfide ion and two protons. Neutral Cu^I^ dithiolate complexes of the type [Cu~4~{S~2~C=(__t__Bu‐fy)}~2~L~4~] [S~2~C=(__t__Bu‐fy) = [2,7‐di‐tert‐butylfluoren‐9‐ylidene)methanedithiolate; L = PPh~3~ (5a), P(C~6~H~4~OMe‐p)~3~ (5b), P__i__Pr~3~ (5d) or L~2~ = dppf (5c)] were obtained by treating 1 with [Cu(NCMe)~4~]PF~6~, the corresponding phosphane, and piperidine in a 1:2:2:1 molar ratio. The reaction of 1 with Cu(ClO~4~)~2~·6H~2~O and (Pr~4~N)OH in a 2:1:2 molar ratio gives the Cu^II^ complex (Pr~4~N)~2~[Cu{S~2~C=(__t__Bu‐fy)}~2~] [(Pr~4~N)~2~6], which readily oxidizes to the Cu^III^ complex Pr~4~N[Cu{S~2~C=(__t__Bu‐fy)}~2~] (Pr~4~N7) in the presence of atmospheric oxygen and moisture. The salt PPN7 [PPN^+^ =(Ph~3~P)~2~N^+^] was obtained from 1, CuCl~2~·2H~2~O, PPNCl, and piperidine in a 2:1:1:2 molar ratio under aerobic conditions. The crystal structures of 3a, 3c·CH~2~Cl~2~, 4a·4Me~2~CO, and 4c·CH~2~Cl~2~ have been determined by X‐ray diffraction studies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)