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Density functional calculations on the Co2(CO)6(SR)2 compounds (R = CH3, CF3) predict both open and butterfly structure types of similar energies. The open Co2(CO)6(μ‐SR)2 structures have non‐planar central Co2S2 units with two bridging RS groups and ca. 3.4 Å Co···Co distances indicating a lack of direct metal–metal bonding. The butterfly Co2(CO)5(μ‐SR)(μ‐CO)(SR) structures have direct Co–Co bonds...
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