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Start Over Author "de Bruin, B." Publisher elsevier bv
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5. Reactivity of Rhodium(II) amido/Rhodium(I) aminyl complexes

Author

Di Zhu, Bas de Bruin, Nan Zhang, Peter H. M. Budzelaar, David E. Herbert, Nicolaas P. van Leest, Zhang, N., Zhu, D., Herbert, D. E., van Leest, N. P., de Bruin, B., Budzelaar, P. H. M., and Nature Inspired Transition Metal Catalysis (HIMS, FNWI)

Subjects
Materials Chemistry2506 Metals and Alloys, Agostic interaction, Dimer, Nitrene, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, law.invention, Rhodium, Inorganic Chemistry, chemistry.chemical_compound, law, Amide, Materials Chemistry, Radical, Physical and Theoretical Chemistry, Electron paramagnetic resonance, Hydrogen atom abstraction, 010405 organic chemistry, Chemistry, 0104 chemical sciences, Monomer, N-C coupling, Aminyl
Abstract

Reaction of the Rh(II) dimer [LRh]2(μ-Br)2 (L = ([2,6-Me2C6H3NCMe]2CH) with the bulky amide LiNH(2,6-iPr2C6H3) leads to a monomeric Rh(II) amide with a T-shape N3Rh arrangement and a pronounced agostic interaction. Reaction with the less bulky LiNH(2,6-Me2C6H3) results in benzylic C-H activation to a binuclear complex with a unique aza-xylylene bridging mode. With LiNHC6H5 we observe initial formation of [LRh]2(μ-NHPh)2 followed by N,C2′ coupling of two anilines. These reactions can be explained based on aminyl radical character of the Rh(II) amides (supported by EPR evidence) and/or involvement of nitrene intermediates.

Published
2018
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