Reactions of carbonyl clusters with potentially tridentate thioethers: Crystal and molecular structures of [Os₄(CO) ₁₃([12]aneS₃)] and [Ru₆(CO)₁₅(μ₄-η²- CO)([12]aneS₃)] [([12]aneS₃) = {(CH₂) ₃S}₃]

The reaction of [Os₃(CO)₁₂ with [12]aneS₃ ([12]aneS₃ {(CH₂)₃S}₃) in octane for 6 h, under reflux, led to isolation of two products [Os₃(CO)₁₁([12]aneS₃)] (1) and [Os₄(CO) ₁₃([12]aneS₃)] (2), while with [Ru₃(CO)₁₂] under similar conditions, in THF, a number of products were obtained, including [Ru₄(CO)₁₁([12]aneS₃)] (3), [Ru₅(CO)₁₃([12]aneS₃)] (4), and [Ru₆(CO)₁₆([12]aneS₃)] (5). An X-ray diffraction study of 2 shows that the macrocycle is coordinated to the 'wingtips' of an Os₄ butterfly through the two electron pairs on one sulphur atom, while in 5 all three sulphur atoms of the macrocycle coordinate to two of the Ru atoms in a spiked edge-bridged tetrahedral metal framework.