The novel nitrosyl-bridged complex [WCp(μ-PBu)(μ-κ:η-NO)(CO)(NO)](BAr) [Ar = 3,5-CH(CF)] was prepared in a multistep procedure starting from the hydride [WCp(μ-H)(μ-PBu)(CO)] and involving the new complexes [WCp(μ-PBu)(CO)](BF), [WCp(μ-PBu)(CO)(NO)](BAr), and [W(μ-κ:η-CH)Cp(μ-PBu)(CO)(NO)] as intermediates, which follow from reactions with HBF·OEt, NO, and MeNO·2HO, respectively. The nitrosyl-bridged cation easily added chloride upon reaction with [N(PPh)]Cl, with concomitant NO rearrangement into the terminal coordination mode, to give [WClCp(μ-PBu)(CO)(NO)], and underwent N-O and W-W bond cleavages upon the addition of CNBu to give the mononuclear phosphinoimido complex [WCp(NPBu)(CNBu)](BAr). Another N-O bond cleavage was induced upon photochemical decarbonylation at 243 K, which gave the oxo- and phosphinito-bridged nitrido complex [WCp(N)(μ-O)(μ-OPBu)(NO)](BAr), likely resulting from a N-O bond cleavage step following decarbonylation.
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| http://dx.doi.org/10.1021/acs.inorgchem.2c02216 | DOI Listing |
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