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.
Reactivity of Rhodium(II) amido/Rhodium(I) aminyl complexes / Zhang, N.; Zhu, D.; Herbert, D. E.; van Leest, N. P.; de Bruin, B.; Budzelaar, P. H. M.. - In: INORGANICA CHIMICA ACTA. - ISSN 0020-1693. - 482:(2018), pp. 709-716. [10.1016/j.ica.2018.06.015]
Reactivity of Rhodium(II) amido/Rhodium(I) aminyl complexes
Budzelaar, P. H. M.
2018
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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.