Antiferromagnetic complexes with metalmetal bonds: Part XXIX. Synthesis and molecular structures of heterochalcogenide binuclear complex [π-(CH3C5H4)Cr(μ-SPh)]2Se and trinuclear mixed-metal cluster [π-(CH3C5H4)2Cr2(μ-SPh)](μ3-S)(μ3-Se)Co(CO)2

[Cp′Cr(CO)2(μ-SPh)]2 (Cp′=π-CH3C5H4) obtained by the interaction of [Cp′Cr(CO)3]2 with Ph2S2 was decarbonylated to [Cp′Cr(CO)(μ-SPh)]2 which reacted with Se powder to give the antiferromagnetic complex [Cp′Cr(μ-SPh)]2(μ-Se) (μeff reduces from 0.79 down to 0.30 μB in the 290–80 K temperature range with exchange parameter −2J=552 cm−1), characterized by X-ray diffraction analysis (CrCr 2.730, CrS 2.635, CrSe 2.401–2.396 Å, CrSeCr 69.4°). Another route to [Cp′Cr(μ-SPh)]2(μ-Se) was the interaction of [Cp′Cr(CO)3]2(μ-Se) with Ph2S2. Treatment of [Cp′Cr(μ-SPh)]2(μ-Se) with Co2(CO)8 results in the mixed-metal heterochalcogenide cluster Cp′2Cr2(μ-SPh)(μ3-S)(μ3-Se)Co(CO)2 characterized by X-ray analysis (CrCr 2.624, CrCo 2.602–2.625, Cr-μ3-S 2.32, Co-μ3-S 2.23, Cr-μ3-Se 2.43, Co-μ3-Se 2.30, Cr-μ-SPh 2.32 Å). The cluster is antiferromagnetic (μeff reduced from 0.73 down to 0.45 μB in the 290–80 K temperature range with exchange parameter −2J=688 cm−1).