Hydrolysis and coordination behavior of ferrocenyl-phosphonodithiolate: Synthesis and structure of Cu4[FcP(OCH3)(μ-S)(μ3-S)]4 [Fc = Fe(η5-C5H4)(η5-C5H5)]

Treatment of the dimeric [FcP(S)(μ-S)]2 [Fc = Fe(η5-C5H4)(η5-C5H5)] with the organic base Et3N in methylene chloride solution resulted in the isolation of a multi-component compound [Et3NH]2[(FcPO2S)2CH2][FcPS(OH)2]2·CH2Cl2 (1·CH2Cl2). The formation of the [(FcPO2S)2CH2]2− anion was due to the dechlorination of methylene chloride, it consists of two [FcPO2S]2− units bridging by a methylene group. Reaction of Na[FcP(OCH3)S2] with equal equivalent of [Cu(MeCN)4][ClO4] in methanol afforded a sole tetranuclear copper(I) complex Cu4[FcP(OCH3)(μ-S)(μ3-S)]4 (2). The neutral complex 2 consists of a crystallographically centrosymmetric tetramer containing four CuS3 arrays each of which has one μ-sulfur and two μ3-sulfur bridges.