Insertion of a Metal Nitride into Carbon−Carbon Double Bonds

Terminal Nitrido and Imido Complexes of the Late Transition Metals

“…In general, Os(VI) nitrido complexes are electrophilic (though organometallic nitrides are nucleophillic) [79] and react with various nucleophiles to form products with new bonds to the nitride nitrogen atom (Scheme 8). [80][81][82][83][84][85][86][87][88][89][90][91][92][93][94][95][96][97][98] The nitrido group in these Os compounds does not display significant nucleophilicity. In fact, Osnitrido species react with electrophilic acylating reagents via ligand substitution pathways that keep the OsN bond intact.…”

Addition of Carbenes to an Osmium(VI) Nitride Complex

“…Osmium(vi) nitride species containing nitrogen-based ligands, such as cis-and trans- [Os VI (N)(tpy)Cl 2 ] + (tpy = 2,2Ј:6Ј,2ЈЈ-terpyridine), [Os VI (N)(tpm)Cl 2 ] + [tpm = tris(1pyrazolyl)methane], [Os VI (N)(Tp)Cl 2 ] [Tp -= hydrotris(1pyrazolyl)borate], and [Os VI (N)(bpy)Cl 3 ] (bpy = 2,2Ј-bi-pyridine), have been shown to exhibit novel electrophilic properties. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] A variety of reagents such as phosphanes, amines, cyanide, azide, Grignard reagents, arylboranes, amine N-oxides, alkenes, and disubstituted benzenethiols have been reported to add to the nitride ligand. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] These reactions are summarised in Scheme 1.…”

Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3− and SO32− in Aqueous Solution

“…The reactivity of transition‐metal nitrido and related imido complexes (M≡N) has received much attention in recent years because they are potentially useful reagents for introducing N atoms into organic molecules; they are also believed to be key intermediates in nitrogen fixation . Notably, extensive work by Meyer and other groups has demonstrated that osmium(VI) nitrido complexes supported by polypyridyl or tris(pyrazolylborate) ligands are highly electrophilic and exhibit oxo‐like reactivity . Our group has been interested in studying the reactivity of nitrido complexes of ruthenium(VI) bearing Schiff base ligands, such as [(L)Ru VI (N)(OH 2 )] + (Ru VI N, L= N,N′ ‐bis(salicylidene)‐ o ‐cyclohexyldiamine dianion, structure is shown in Figure ) .…”

“…[1] Notably, extensive work by Meyer and other groups has demonstrated that osmium(VI) nitrido complexes supported by polypyridyl or tris(pyrazolylborate) ligands are highly electrophilic and exhibit oxo-like reactivity. [2][3][4][5] Our group has been interested in studying the reactivity of nitrido complexes of ruthenium(VI) bearing Schiff base ligands, such as [(L)Ru VI (N)(OH 2 )] + (Ru VI N, L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion,s tructure is shown in Figure 1). [6] This complex is found to be highly electrophilic/oxidizing.…”