Chemistry of a Nitrosyl Ligand κ:η-Bridging a Ditungsten Center: Rearrangement and N-O Bond Cleavage Reactions.

ABSTRACT: The novel nitrosyl-bridged complex [W₂Cp₂(μ-P^tBu₂)(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^tBu₂)(CO)₄] and involving the new complexes [W₂Cp₂(μ-P^tBu₂)(CO)₄](BF₄), [W₂Cp₂(μ-P^tBu₂)(CO)₂(NO)₂](BAr₄), and [W₂(μ-κ:η⁵-C₅H₄)Cp(μ-P^tBu₂)(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-P^tBu₂)(CO)(NO)₂], and underwent N-O and W-W bond cleavages upon the addition of CN^tBu to give the mononuclear phosphinoimido complex [WCp(NP^tBu₂)(CN^tBu)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^tBu₂)(NO)](BAr₄), likely resulting from a N-O bond cleavage step following decarbonylation.

SUBMITTER: Alvarez MA 

PROVIDER: S-EPMC9516685 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature