Terminal Nitrido and Imido Complexes of the Late Transition Metals

Abstract

Compounds that contain a late transition metal-nitrogen multiple bond represent important reactive intermediate species in many useful organic and inorganic transformations. In order to understand the role that these intermediates play in reactions, it is important to have a full understanding of their electronic structure. This paper reviews the known structural motifs that occur in late transition metal nitrido and imido compounds, and provides a correlation between geometric structure and electronic structure. Also, intermediate species that have been postulated but not yet isolated are discussed, as these compounds represent exciting targets for further efforts in synthetic inorganic chemistry.

Trapping of an NiII Sulfide by a CoI Fulvene Complex

“…1 This class of compounds tend to be highly reactive, [2][3][4] and as a result, only a few well characterized late metal terminal chalcogenides are known, including [Ir (PCN = C 6 H 3 [CH 2 P(tBu) 2 ](CH 2 CH 2 NMe 2 )). 5,6 A number of late transition metal carbene (CR 2 2-), nitrene (NR 2-), nitride (N 3-), and phosphinidene (PR 2-) complexes have also been reported in recent years.…”

C–H Functionalization Reactivity of a Nickel–Imide

“…4 Later, Cenini and co-workers isolated the N-aryl analogue (porphyrin)Ru(NAr F ) 2 (Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) that reacts with C−H bonds of modest strength such as the allylic C−H bond of cyclohexene. 12 Nickel imides have played key roles in the renaissance of late metal imido chemistry 1 ignited by the 2001 report of the three coordinate terminal imide (dtbpe)NiNAr (Ar = 2,6-iPr 2 C 6 H 3 ) 13 by Mindiola and Hillhouse, which engages in stoichiometric nitrene group transfer to isocyanides, 14 CO, 14 and ethylene 15 ( Figure 1). Formed via η 2 -azide adducts (dtbpe)Ni(η 2 -N 3 R), 16 the nickel(II) imides (dtbpe)NiNR (R = 1-adamantyl (Ad), 2,4,6-Me 3 C 6 H 2 (Mes)) 16 may be oxidized to their cationic nickel(III) analogues {(dtbpe)Ni NR} + , which exist in both S = 1/2 (R = Ad and Mes) and S = 3/2 states (R = Ad) ( Figure 1).…”

“…Metal−imide (nitrene) intermediates, [M]NR′, 1 have been implicated in many catalytic C−H amination reactions that allow the atom economical introduction of nitrogen atoms into organic molecules without traditional functional group manipulations.…”

Detection of Indistinct Fe−N Stretching Bands in Iron(V) Nitrides by Photodissociation Spectroscopy

“…[1][2][3][4][5] The spectroscopic data on iron-oxo compounds, including the FeÀO stretching frequency, are well established; [6,7] however, the information about FeÀN bonds is still scarce. Spectral signatures of the FeÀN bond depend on both the oxidation state of iron centre and the symmetry of the surrounding ligand field.…”