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Alvarez, M. Angeles; García, M. Esther; García-Vivó, Daniel; Guerra, Ana M.; Ruiz, Miguel A.; Falvello, Larry R.
Inorganic chemistry, 09/2022, Letnik: 61, Številka: 38Journal Article
The novel nitrosyl-bridged complex W2Cp2(μ-P t Bu2)(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-P t Bu2)(CO)4 and involving the new complexes W2Cp2(μ-P t Bu2)(CO)4(BF4), W2Cp2(μ-P t Bu2)(CO)2(NO)2(BAr4), and W2(μ-κ:η5-C5H4)Cp(μ-P t Bu2)(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)2Cl, with concomitant NO rearrangement into the terminal coordination mode, to give W2ClCp2(μ-P t Bu2)(CO)(NO)2, and underwent N–O and W–W bond cleavages upon the addition of CN t Bu to give the mononuclear phosphinoimido complex WCp(NP t Bu2)(CN t Bu)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-OP t Bu2)(NO)(BAr4), likely resulting from a N–O bond cleavage step following decarbonylation.
