This account presents the diverse reactivity of nitridoruthenium() complexes with nucleophilic, electrophilic and oxidizing agents. [Ru VI (N)(L 1 )Cl] (1) [H 2 L 1 = 2,6-bis(2,2-diphenyl-2-hydroxyethyl)pyridine] reacted with excess phosphines such as PPh 3 , PPhMe 2 and dppe to give [Ru III (HL 1 )(PPh 3 )Cl 2 ] (2a), [Ru III (L 1 )(PPhMe 2 ) 2 Cl] (2b) and [Ru III (L 1 )(dppe)Cl] (2c), respectively. In the presence of py or Hpz, 1 was converted to [Ru III (L 1 )(py) 2 Cl] (3a) and [Ru III (L 1 )(Hpz) 3 ]Cl (3b), respectively. A dinuclear µ-nitridoruthenium complex, [Ru IV (L 1 )Cl 2 (µ-N)Ru VI (L 1 )-(C 8 H 10 N)Cl] (4), was obtained by treating 1 with 2,6-dimethylaniline. Based on X-ray crystallographic study, the compound is characterized by an unsymmetrical Ru-N᎐ ᎐ ᎐ Ru moiety with the measured Ru-N distances being 1.661(5) and 1.837(5) Å. Complex 1 reacted with dmf to give [Ru III (HL 1 )(dmf )Cl 2 ] (5) in 17% yield. Excess (Me 3 O)BF 4 reacted with 1 to give a dinuclear µ-OH ruthenium complex, [Ru 2 (N) 2 (L 1 ) 2 (OH)]PF 6 (6). The measured Ru-O (OH) distance is 1.984(3) Å and the average Ru-O-Ru angle was found to be 100.4(2)Њ. Other nitrido-metal complexes, [n-Bu 4 N]-[M VI (N)(L)] [L = L 2 and L 3 ; M = Os and Ru; H 4 L 2 = 1,2-dichloro-4,5-bis(2-hydroxybenzamido)benzene, H 4 L 3 = 1,2-bis(2-hydroxybenzamido)benzene], underwent ligand protonation to form [M VI (N)(HL)] complexes, which have been characterized by X-ray crystallography. Oxidation of [n-Bu 4 N][Os VI (N)(L 2 )] by PhI(OAc) 2 produced [n-Bu 4 N][Os VI (N)(L 2 O 2 )] ( 8) in 10% yield. X-ray structure analysis of 8 showed that the coordinated phenoxy moiety was converted to a benzoquinone moiety while the Os᎐ ᎐ ᎐ N group remained intact.
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