73440-06-9Relevant academic research and scientific papers
Inter- and Intra-molecular Ligand-exchange and -rearrangement Reactions of Tetra-azadiene Complexes of Nickel, Platinum, and Cobalt
Overbosch, Peter,Koten, Gerard van,Vrieze, Kees
, p. 1541 - 1548 (2007/10/02)
Tetra-azadiene-exchange and -rearrangement reactions have been observed for both and 5-C5H5)> (R2=1,4-diaryl) complexes.The reactions of or 5-C5H5)> with aryl azides lead to substitution of the tetra-azadiene ligands.Reactions of or 5-C5H5)> with aryl azides R'N3 produced platinium and nickel complexes with non-symmetrical RN4R' ligands.All products arising from these reactions were identified by field desorption mass spectrometry and/or h.p.l.c.Four mechanisms which can account for the nature of the observed products, the product distributions, and reaction times are discussed.Transient aryl-nitrene species are proposed as key intermediates in these reactions.
Synthesis and reactivity of bis(1,4-diaryltetraazabutadiene)nickel complexes. Crystal and molecular structure of bis[1,4-bis(3,5-dimethylphenyl)tetraazabutadiene]nickel
Overbosch, Peter,Van Koten, Gerard,Overbeek
, p. 2373 - 2378 (2008/10/08)
Bis(tetraazabutadiene)nickel complexes, [Ni(Ar2N4)2], have been prepared by reactions of bis(1,5-cyclooctadiene)nickel or bis(cyclopentadienyl)nickel with aryl azides (Ar = 4-MeC6H4, 4-MeOC6H4, 4-ClC6H4, and 3,5-Me2C6H3). The reaction with bis(cyclopentadienyl)nickel proceeds via [Ni(Ar2N4)(η5-C5H5)]. The crystal and molecular structure of bis[1,4-bis(3,5-dimethylphenyl)tetraazabutadiene]nickel, which is the first example of a bis(tetraazabutadiene)metal complex, have been determined by a single-crystal X-ray diffraction study. Crystals are tetragonal, space group P42/n, with Z = 2 in a unit cell of dimensions a = b = 9.677 (1) and c = 16.601 (1) A?. The final R value is 0.034 for 1307 reflections. The nickel atom has a pseudotetrahedral geometry with two planar Ar2N4 ligands orientated perpendicular to each other. Furthermore the three N-N bond distances are nearly equal with a mean value of 1.322 A?. On the basis of these structural features the compounds are formulated as 18e Ni0 species. Bis[1,4-bis(4-tolyl)tetraazabutadiene]nickel reacts with tert-butyl isocyanide to give [Ni[1,4-(4-MeC6H4)2N4](t-BuNC) 2]. The latter product could also be prepared via the 1/1 reaction of [Ni[1,4-(4-MeC6H4)2N4]2] with [Ni(t-BuNC)4] in the presence of excess t-BuNC.
