Reactivity of Rhodium(II) amido/Rhodium(I) aminyl complexes

Abstract

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.

Growth and Properties of Intentionally Carbon‐Doped GaN Layers

“…They allow for the investigation of intentional carbon doping without interference from unintentionally incorporated carbon. Doping of GaN with propane in HVPE revealed that carbon together with oxygen and hydrogen results in at least two transitions of yellow defect luminescence (YL) with a deep acceptor involved . An investigation in rf plasma‐assisted MBE with CBr 4 as carbon source revealed that carbon in concentrations up to 10 19 cm −3 has no negative influence on structural properties of GaN but compensates Si donors .…”

A Vanadium Methylidene

“…Using the V III precursor, [(PNP)VCl 2 ], 16 we sought to install a sterically encumbering robust ancillary ligand to offer more kinetic stabilization and discourage decomposition pathways. Accordingly, transmetalation of [(PNP)VCl 2 ] with Li(THF)(NHAr) 17 in toluene cleanly produced red crystals of [(PNP)V(NHAr)Cl] (1) in 79% crystalline yield (Scheme 1).…”

“…Using the V III precursor, [(PNP)­VCl 2 ], we sought to install a sterically encumbering robust ancillary ligand to offer more kinetic stabilization and discourage decomposition pathways. Accordingly, transmetalation of [(PNP)­VCl 2 ] with Li­(THF)­(NHAr) in toluene cleanly produced red crystals of [(PNP)­V­(NHAr)­Cl] ( 1 ) in 79% crystalline yield (Scheme ). To install a methylidene, we then treated 1 with a Grignard MgCl­(CH 3 ) in toluene at room temperature to cleanly afford [(PNP)­V­(NHAr)­(CH 3 )] ( 2 ) in 80% yield (Scheme ).…”