Reaction of the Rh(II) dimer [LRh] 2 (μ-Br) 2 (L = ([2,6-Me 2 C 6 H 3 NCMe] 2 CH) with the bulky amide LiNH (2,6-i Pr 2 C 6 H 3) leads to a monomeric Rh(II) amide with a T-shape N 3 Rh arrangement and a pronounced agostic interaction. Reaction with the less bulky LiNH(2,6-Me 2 C 6 H 3) results in benzylic C-H activation to a binuclear complex with a unique aza-xylylene bridging mode. With LiNHC 6 H 5 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.
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