Antiferromagnetic complexes with metal–metal bonds.: Part XXX. Synthesis and molecular structures of the antiferromagnetic adducts [Cp′Cr(μ-SPh)]2(μ3-Se).ML (Cp′=η5-CH3C5H4, ML=Fe3(μ3-S)2(CO)8, Mn2(CO)9, Mn2(CO)8), paramagnetic complexes Cp′Cr(μ-SPh)3Mn(C

The photochemical reactions of antiferromagnetic heterochalcogenic complex [Cp′Cr(μ-SPh)]2(μ-Se) (1) (Cp′=η5-CH3C5H4) with Fe3(μ3-Se)2(CO)9 or Mn2(CO)10 at room temperature gives new mixed-metal heterochalcogenic clusters [Cp′Cr(μ-SPh)]2(μ3-Se)Fe3(μ3-Se)2(CO)8 (2), [Cp′Cr(μ-SPh)]2(μ3-Se)Mn2(CO)9 (3) and [Cp′Cr(μ-SPh)]2(μ4-Se)Mn2(CO)8 (4) which are antiferromagnetic (−2J=256, 230 and 324 cm−1, respectively) and characterized by X-ray diffraction analysis (2: Cr–Cr 2.763(1) Å; Fe–Fe 2.6184(9) and 2.706(1) Å; Cr–Se 2.447, 2.460 Å; 3: Cr–Cr 2.762 Å; Mn–Mn 2.920 Å; Cr–Se 2.447, 2.460 Å; 4: Cr–Cr 2.816 Å, Mn–Mn 2.835 Å, Cr–Se 2.464 Å). The photochemical reaction of 1 and Mn2(CO)10 at higher temperature gives the paramagnetic complex Cp′Cr(μ-SPh)3Mn(CO)3 (5) with a weak Cr–Mn bond (3.0239 Å). The new heterochalcogenic complex [Cp′Cr(μ-SPh)]2(μ-Te) (6) which obtained at the interaction of [Cp′Cr(CO)(μ-SPh)]2 with Te and was studied by X-ray method (Cr–Cr 2.772 Å, Cr–S 2.359 Å, Cr–Te 2.601–2.607 Å, Cr–Te–Cr 64.3°), reacted with Co2(CO)8 with formation of the diamagnetic mixed-metal heterochalcogenic cluster [Cp′2Cr2(SPh)](μ3-S)(μ3-Te)Co(CO)2 (7) (Cr–Cr 2. 646 Å, Cr–Co 2.627 Å–2.623 Å, Cr–μ3-S 2.282–2.299 Å, Co–μ3-S 2.199 Å, Cr–μ3-Te 2.630–2.618 Å, Co–μ3-Te 2.466 Å, Cr–μ-SPh 2.335 Å). The role of super-exchange spin–spin interaction through the chalcogen bridge atom is discussed.