doi:10.1021/acs.inorgchem.2c02216engAlvarez, M. AngelesGarcía, M. EstherGarcía-Vivó, DanielGuerra, Ana M.Ruiz, Miguel A.Falvello, Larry R.Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactionsART-2022-130638The 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.2022http://zaguan.unizar.es/record/11990810.1021/acs.inorgchem.2c02216http://zaguan.unizar.es/record/119908oai:zaguan.unizar.es:119908info:eu-repo/grantAgreement/ES/MCINN-FEDER/PGC2018-093451-B-I00info:eu-repo/grantAgreement/ES/MCINN-FEDER/PGC2018-097366-B-I00Inorganic Chemistry 61, 38 (2022), 14929-14933byhttp://creativecommons.org/licenses/by/3.0/es/info:eu-repo/semantics/openAccess