Alkylation of osmium(VI) nitrido complexes: reaction of [Os(N)R4][NBu4] with [Me3O][BF4] and the x-ray crystal structures of [Os(N)(CH2SiMe3)4] [NBu4] and [Os(NMe)(CH2SiMe3)4]

Assembly of Molybdenum/Titanium μ-Oxo Complexes via Radical Alkoxide C−O Cleavage

“…The intent was to deliver Me + to the terminal nitrido function with this regimen. Such alkylations have been successful for a select few terminal nitrido complexes, according to the literature . (Protonation reactions of terminal nitrido ligands are also known, , although the “lone-pair” of terminal molybdenum(VI) nitrido ligands is decidedly nonbasic …”

Nitrido-ruthenium(vi) and -osmium(vi) complexes of multianionic chelating (N, O) ligands. Reactions with nucleophiles, electrophiles and oxidizing agents

“…Reactions of nitrido ligand in late transition metal-nitrido complexes toward electrophilies are sparse in the literature. 22 In contrast, the nitrido ligand in some early transition metalnitrido complexes [e. 25 In this work, we are interested to explore the reactivity of nitridoruthenium() complexes toward electrophilic reagents (Scheme 4). When 1 was treated with excess (Me 3 O)BF 4 in CH 2 Cl 2 , a red crystalline solid was isolated and characterized by X-ray crystal analysis to be [Ru VI 2 (N) 2 (L 1 ) 2 (OH)]PF 6 (6), which contains two Ru᎐ ᎐ ᎐ N groups and the two ruthenium atoms are bridged by a hydroxyl group.…”

Synthesis of Hydride and Alkyl Compounds Containing the Cp*Os(η3-allyl) Fragment. Crystal Structures of Cp*Os(η3-C8H13)Br2and [Cp*Os(η3-C4H7)Me(H2O)][BF4]

“…The compounds have the stoichiometry [NBu 4 ][OsN(CH 2 SiMe 3 ) 2 Cl 2 ] and [NBu 4 ][OsNR 4 ], where R is CH 2 CMe 3 , CH 2 Ph, or Me . The nitrido tetraalkylosmate(VI) anions can be methylated at the nitrogen atom with methyl iodide to give the corresponding neutral methylimido complexes . The halide ligands in the partially alkylated compound [OsN(CH 2 SiMe 3 ) 2 Cl 2 - ] can be replaced with oxygen-, sulfur-, or phosphorus-containing ligands to afford other classes of high-valent osmium alkyls. − More recently, Schrock and co-workers synthesized complexes with the general formulas Os(NAr) 2 R 2 and OsO(NAr)R 2 (NAr = N-2,6- i -Pr 2 C 6 H 3 ; R = CH 2 CMe 3 , CH 2 CMe 2 Ph, CH 2 SiMe 3 ). , …”