Synthesis and Structural Characterization of the μ-η¹:η⁵-Ph₂PC₅H₄ Ligand-Containing Transition-Metal Cluster and Dinuclear Complexes (μ-η¹:η⁵-Ph₂PC₅H₄)(μ₃-S)MFeCo(CO)₇ (M = Mo, W), (μ-η¹:η⁵-Ph₂PC₅H₄)(μ₃-RC)MCo₂(CO)₇ (M = Mo, W; R = Me, Ph), and (μ-η¹:η⁵-Ph₂PC₅H₄)CpMo₂(CO)₅ Obtained from the Studied Isolobal Displacement Reactions

Abstract

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-η1:η5-Ph2PC5H4-containing tetrahedral clusters (μ-η1:η5-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-η1:η5-Ph2PC5H4)(μ3-MeC)MCo2(CO)7 (3, M = Mo; 4, M = W) and (μ-η1:η5-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-η1:η5-Ph2PC5H4)CpMo2Co2(CO)9 (7) was not produced, but instead the dinuclear complex (μ-η1:η5-Ph2PC5H4)CpMo2(CO)5 (8) was obtained unexpectedly. While 1−6 and 8 have been characterized by elemental analysis and spectroscopy, as well as by X-ray crystallography for 1−3 and 8, the possible pathways for formation of these products are suggested.