Monomeric (pentamethylcyclopentadienyl)iridium imido compounds: synthesis, structure, and reactivity

N‐Heterocyclic Carbene Functionalized Iridium Phosphinidene Complex [Cp*(NHC)IrPMes*]: Comparison of Phosphinidene, Imido, and Carbene Complexes

“…The imido complex 5 exhibits a short 1.884 ä IrN double bond which is elongated with respect to known Ir N triple bonds (1.71 ± 1.75 ä). [13] A remarkable structural aspect of 5 …”

“…1 H, 13 C and 31 P NMR spectra were recorded at 300 K on a Bruker Avance 250 spectrometer at 250.13, 62.90 and 101.25 MHz, respectively. 1 H NMR spectra were referenced to CHCl 3 (d 7.27) [31] 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, [3] and [LiPHMes*] ¥ 3 THF [32] were prepared according to literature procedures.…”

“…Furthermore, structural and bonding properties for the iridium phosphinidene parent complex that contains the imidazol-2-ylidene ligand is evaluated theoretically, and comparisons are made with analogous alkylidene and imido complexes. The transition metal iridium is used because similar alkylidene, [11,12] imido, [13] phosphinidene, [9] as well as N-heterocyclic carbene complexes [14] are known experimentally for iridium. [14] and confirms the presence of the carbene moiety in 2.…”

Multiple‐Bond Metathesis Mediated by Sterically Pressured Uranium Complexes

“…For example, carbodiimide species 7 quantitatively reacts with CH 2 Cl 2 and CH 3 I to yield the free carbodiimides There have been previous reports of a nitrene-group transfer from metal imido complexes to p-accepting ligands, such as CO for example, thus yielding various organic isocyanates and the corresponding reduced metal carbonyl species [28][29][30][31] and the archetypal Bergman [(Cp*)Ir(N(CO)tBu)(CO)] (Cp* = pentamethylcyclopentadienyl) complex with an h 2 :C,N bound CO fragment. [32] Chirik and co-workers recently reported the reaction of [(Cp'') 2 Ti(NSiMe 3 )] (Cp'' = h 5 -C 5 H 3 -1,3-(SiMe 3 ) 2 ) with CO to yield Me 3 SiÀNCO and the two-electron-reduced [(Cp'') 2 Ti(CO) 2 ] complex. [31] The discovery of metal imido complexes MNR that react with paccepting ligands L to form one-electron-reduced nucleophilic h 1 -MÀNL species, as reported herein, represents a new type of metal-imido transformation.…”

Formation of CC and CN Bonds in NiII Ketimide Complexes via Transient NiIII Aryl Imides

“…[12][13][14] In fact, while McGlinchey and Stone [15] reported in 1970 the generation of [(Ph 2 MeP) 2 M = NCF 2 CFHCF 3 ](M=Pd, Pt) incorporating an imido ligand, the number of subsequent reports was quite small until recently. In the late 1980s and 1990s Bergman and co-workers described the synthesis and reactivity of Ir [16,17] and Os imides [18,19] while Burrell and Steedman [20,21] reported the complex [(h 6 -benzene)-Ru = NAr] (Ar = 2,6-iPr 2 C 6 H 3 ). In 2001, Mindiola and Hillhouse [22] showed the deprotonation of the corresponding amide to give the terminal Ni II imide [(tBu 2 PCH 2 CH 2 PtBu 2 )Ni=NAr], which undergoes reactions with CO and benzyl isocyanide as well as ethylene to give the corresponding carbodiimide [22,23] and aziridines, [24] respectively.…”