Chemistry of a Nitrosyl Ligand κ:η-Bridging a Ditungsten Center: Rearrangement and N-O Bond Cleavage Reactions
M Angeles Alvarez1, M Esther García1, Daniel García-Vivó1
1Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, Oviedo E33071, Spain.
Abstract:
The novel nitrosyl-bridged complex [W2Cp2(μ-PBu2)(μ-κ:η-NO)(CO)(NO)](BAr4) [Ar = 3,5-C6H3(CF3)2] was prepared in a multistep procedure starting from the hydride [W2Cp2(μ-H)(μ-PBu2)(CO)4] and involving the new complexes [W2Cp2(μ-PBu2)(CO)4](BF4), [W2Cp2(μ-PBu2)(CO)2(NO)2](BAr4), and [W2(μ-κ:η5-C5H4)Cp(μ-PBu2)(CO)(NO)2] as intermediates, which follow from reactions with HBF4·OEt2, NO, and Me3NO·2H2O, respectively. The nitrosyl-bridged cation easily added chloride upon reaction with [N(PPh3)2]Cl, with concomitant NO rearrangement into the terminal coordination mode, to give [W2ClCp2(μ-PBu2)(CO)(NO)2], and underwent N-O and W-W bond cleavages upon the addition of CNBu to give the mononuclear phosphinoimido complex [WCp(NPBu2)(CNBu)2](BAr4). Another N-O bond cleavage was induced upon photochemical decarbonylation at 243 K, which gave the oxo- and phosphinito-bridged nitrido complex [W2Cp2(N)(μ-O)(μ-OPBu2)(NO)](BAr4), likely resulting from a N-O bond cleavage step following decarbonylation.
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