ABSTRACT
Three five-coordinate iron(IV) imide complexes have been synthesized and characterized. These novel structures have disparate spin states on the iron as a function of the R-group attached to the imide, with alkyl groups leading to low-spin diamagnetic (S=0) complexes and an aryl group leading to an intermediate-spin (S=1) complex. The different spin states lead to significant differences in the bonding about the iron center as well as the spectroscopic properties of these complexes. Mössbauer spectroscopy confirmed that all three imide complexes are in the iron(IV) oxidation state. The combination of diamagnetism and 15 N labeling allowed for the first 15 N NMR resonance recorded on an iron imide. Multi-reference calculations corroborate the experimental structural findings and suggest how the bonding is distinctly different on the imide ligand between the two spin states.
ABSTRACT
Multiple distinct oxidative group transfer reactions to low valent chromium were examined. Six new chromium complexes were prepared from a highly electronically unsaturated Cr(II) square planar complex that was supported by a macrocyclic tetracarbene ligand. This complex's reactivity with Me3NO and disparate azides was investigated. The reaction with Me3NO generated a highly stable Cr(IV)-oxo complex. Less bulky organic azides such as p-tolyl and n-octyl azides gave rise to metallotetrazenes, while more sterically demanding mesityl and adamantyl azides generated Cr(IV)-imido complexes. The reaction of the square planar Cr(II) complex with TMS-azide yielded the first linearly bridging nitrido chromium species. Reductive group transfer was explored for a Cr(IV)-imido complex, and organic products, such as aziridines, were formed after addition. Cr(IV) imidos and oxos are quite rare, while tetrazenes and bridging nitridos are virtually unknown. This is the most detailed study on oxidative group transfer reactions using chromium based complexes on a single auxiliary ligand to date.