om070020a_si_002.cif (30.78 kB)

Synthesis and Structural Characterization of the μ-η15-Ph2PC5H4 Ligand-Containing Transition-Metal Cluster and Dinuclear Complexes (μ-η15-Ph2PC5H4)(μ3-S)MFeCo(CO)7 (M = Mo, W), (μ-η15-Ph2PC5H4)(μ3-RC)MCo2(CO)7 (M = Mo, W; R = Me, Ph), and (μ-η15-Ph2PC5H4)CpMo2(CO)5 Obtained from the Studied Isolobal Displacement Reactions

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posted on 02.04.2020, 15:23 by Li-Cheng Song, Guang-Ao Yu, Yang Liu, Bang-Shao Yin, Xiao-Guang Zhang, Qing-Mei Hu
The isolobal displacement reaction of tetrahedral cluster (μ3-S)FeCo2(CO)9 with isolobal reagents η5-Ph2PC5H4(CO)3MLi (M = Mo, W) in THF at about 60 °C was found to give the μ-η15-Ph2PC5H4-containing tetrahedral clusters (μ-η15-Ph2PC5H4)(μ3-S)MFeCo(CO)7 (1, M = Mo; 2, M = W), whereas tetrahedral clusters (μ3-RC)Co3(CO)9 (R = Me, Ph) reacted with η5-Ph2PC5H4(CO)3MLi under the same conditions to afford the corresponding tetrahedral clusters (μ-η15-Ph2PC5H4)(μ3-MeC)MCo2(CO)7 (3, M = Mo; 4, M = W) and (μ-η15-Ph2PC5H4)(μ3-PhC)MCo2(CO)7 (5, M = Mo; 6, M = W). However, it was found that when tetrahedral cluster CpMoCo3(CO)11 reacted with isolobal reagent η5-Ph2PC5H4(CO)3MoLi under similar conditions, the corresponding tetrahedral cluster (μ-η15-Ph2PC5H4)CpMo2Co2(CO)9 (7) was not produced, but instead the dinuclear complex (μ-η15-Ph2PC5H4)CpMo2(CO)5 (8) was obtained unexpectedly. While 16 and 8 have been characterized by elemental analysis and spectroscopy, as well as by X-ray crystallography for 13 and 8, the possible pathways for formation of these products are suggested.