Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions

Alvarez, M. Angeles ; García, M. Esther ; García-Vivó, Daniel ; Guerra, Ana M. ; Ruiz, Miguel A. ; Falvello, Larry R. (Universidad de Zaragoza)

Resumen: The novel nitrosyl-bridged complex [W2Cp2(μ-PtBu2)(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-PtBu2)(CO)4] and involving the new complexes [W2Cp2(μ-PtBu2)(CO)4](BF4), [W2Cp2(μ-PtBu2)(CO)2(NO)2](BAr4), and [W2(μ-κ:η5-C5H4)Cp(μ-PtBu2)(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-PtBu2)(CO)(NO)2], and underwent N–O and W–W bond cleavages upon the addition of CNtBu to give the mononuclear phosphinoimido complex [WCp(NPtBu2)(CNtBu)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-OPtBu2)(NO)](BAr4), likely resulting from a N–O bond cleavage step following decarbonylation.

Idioma: Inglés

DOI: 10.1021/acs.inorgchem.2c02216

Año: 2022

Publicado en: Inorganic Chemistry 61, 38 (2022), 14929-14933
ISSN: 0020-1669

Factor impacto JCR: 4.6 (2022)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 5 / 42 = 0.119 (2022) - Q1 - T1

Factor impacto CITESCORE: 8.0 - Chemistry (Q1)

Factor impacto SCIMAGO: 0.997 - Chemistry (miscellaneous) (Q1) - Physical and Theoretical Chemistry (Q1) - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/MCINN-FEDER/PGC2018-093451-B-I00
Financiación: info:eu-repo/grantAgreement/ES/MCINN-FEDER/PGC2018-097366-B-I00

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)