Preparation and reactivity of half-sandwich hydrazine complexes of ruthenium and osmium

Azo Complexes of Osmium(II): Preparation and Reactivity of Organic Azide and Hydrazine Derivatives

“…We are interested in the chemistry of diazo and triazo complexes of transition metals and have reported the synthesis and reactivity of hydrazine, diazene, diazenido, and triazene derivatives of Mn and Fe triads and, recently, the first benzylazide complexes of iridium stabilized by phosphites P(OR) 3 as supporting ligands. We thought of extending our studies on azo complexes with the additional aim of preparing organic azide complexes of the iron triad.…”

Synthesis and X-ray studies of ruthenium(II) complexes containing hydrazine and benzyl isocyanide ligands

“…This is partly due to the interest in different coordination modes offered by hydrazine complexes [7][8][9][10] and also to the importance of hydrazine in the dinitrogen fixation process [11]. The coordination of hydrazine to metal centers is usually through the nitrogen in a monodentate fashion but in a few cases, a bridging bidentate coordination mode can be adopted [11].…”

Base-Induced Dehydrogenation of Ruthenium Hydrazine Complexes

“…The crystal structure (Figure 3) clearly shows the side-on bound nature of the hydrazine ligand, the uncoordinated phosphine arm (P3), and the fact that the chloride ligand is trans to the central phosphorus (P4). The geometry about ruthenium is that of a severely distorted octahedron with an acute N1−Ru1−N2 angle of 39.66 (6)°and angles of 113.45 (6), 108.36 (6), and 98.53 (5)°for N2−Ru1− P1, N1−Ru1−P2, and P1−Ru1−P2, respectively. The Ru−N bond lengths of 2.1242 (18) and 2.1324 (18) Å are within the range for previously reported Ru hydrazine complexes (2.101− 2.273 Å).…”

“…There has been recent interest in the synthesis of iron hydrazine and diazene complexes as well as studies into their interconversions as possible models of the interaction at nitrogenase . There has also been interest in the synthesis of phenyl- and methyl-substituted hydrazine and diazene complexes of iron as well as ruthenium − since these are considered more stable analogues of the parent unsubstituted species and may be able to shed light on the chemistry and properties of metal hydrazines and diazenes.…”

“…The chloro ligand is trans to the central phosphine (P4) indicating that geometric isomer (a) was crystallized preferentially. The distorted octahedral geometry about ruthenium is shown by the acute N1−Ru1−N2 angle of 39.54 (16)°as well as angles for N2−Ru1−P1, N1− Ru1−P2, and P1−Ru1−P2 of 114.79 (12), 107.62 (12), and 98.06 (5), respectively. Short contacts were observed from the N atoms of the methylhydrazine ligand to the chloride counterion (3.119−3.126 Å), and this may contribute to the stability of the complex in the solid state.…”