trans-[(Mo₆Cl₈)(C₇H₇)₄{P(n-C₄H₉)₃}₂] and trans-[(Mo₆Cl₈)(C₈H₅)₄{P(n-C₅H₁₁)₃}₂].2C₇H₈

The title compounds, tetrabenzyl-2κC,3κC,4κC,5κC-octa-μ₃-chloro-bis(tributylphosphine)-1κP,6κP-octahedro-hexamolybdenum(12Mo—Mo), (1) and tetrakis(phenylethynyl)-2κC,3κC,4κC,5κC-octa-μ₃-chloro-bis(tripentylphosphine)-1κP,6κP-octahedro-hexamolybdenum(12Mo—Mo)-toluene (1/2), (2), containing octahedral Mo clusters with four σ-C ligands, were prepared by the reaction of trans-[(Mo₆Cl₈)Cl₄(PR₃)₂] with tribenzylaluminium and tris(phenylethynyl)aluminium, respectively, and their structures determined. The octahedral Mo₆ cores of both compounds are on inversion centres and are almost regular. Average interatomic distances in the clusters for (1) are Mo—Mo(edge) = 2.618, Mo...Mo(opposite) = 3.703, Mo—Cl = 2.477 and Mo—C = 2.26 Å, and for (2) are Mo—Mo(edge) = 2.626, Mo...Mo(opposite) = 3.714 and Mo—C = 2.13 Å.

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