Abstract
Two equivalents of W 2COT(NMe 2) 4 react with eight equivalents of methanol, ethanol, or n-propanol to form the corresponding tetranuclear alkoxide clusters: [W 2COT(OR) 4] 2 where R=Me, Et, or Pr. Single-crystal X-ray diffraction studies on the ethoxide and propoxide compounds reveal centrosymmetric molecules containing two [W 2(μ-η 5,η 5-COT)(μ-OR)(OR) 2] fragments. Each fragment has a W–W bond length of ca. 2.39 Å and is connected to the other by a pair of symmetrically-bridging alkoxides. These bridging alkoxides are not cleaved in the presence of σ-donors thf and pyridine, or π-acceptor 2-butyne. NMR data suggest that this structure is maintained in solution. Unlike in the related dinuclear alkoxides, W 2COT(OR) 4 [where R=CH 2Bu t , Pr i and Bu t ], the COT ligands are not fluxional at ambient temperature. The structural similarities between [W 2COT(OPr) 4] 2, W 2COT(OBu t ) 4, and W 4(H) 2(OPr i ) 14 are discussed.
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