Interaction of manganese(II), iron(II), cobalt(II), nickel(II), copper(II) and zinc(II) with acetylhydrazine, formed in situ; first crystal structure of tris(acetylhydrazine) nickel(II) perchlorate

Abstract

A series of transition metal complexes of the type [M(ah) 3 ](ClO 4 ) 2 (1-6) [M ¼ Mn II , Fe II , Co II , Ni II , Cu II and Zn II , ah ¼ acetylhydrazine] have been prepared by the reaction of M(ClO 4 ) 2 AE 6H 2 O with acetylhydrazine formed in situ by the reaction of hydrazine hydrate and acetylsalicylic acid methyl ester. The chelating behaviour of acetylhydrazine and overall geometry of these complexes have been spectroscopically investigated by means of FT-IR, 1 H-n.m.r. and electronic spectral techniques, as well as by elemental analysis data, molar conductance values and magnetic susceptibility measurements. Single X-ray structure determination of complex (4) revealed three acetylhydrazine ligands coordinated to nickel ion in a bidentate manner maintaining an octahedral environment. In all other complexes too, an octahedral geometry has been proposed on the basis of results obtained by various physico-chemical studies.

Triggering N2 uptake via redox-induced expulsion of coordinated NH3 and N2 silylation at trigonal bipyramidal iron

“…These vibrations are broadened and shifted in solid-state spectra from that of their non-hydrogen bonded hydrazine derivatives { 6a }{B(ArF) 4 } and { 6b }{B(ArF) 4 }. Hydrazine adducts with an η 1 -binding mode to 5-coordinate metal complexes are uncommon iv,xix,xx,xxi,xxii,xxiii,xxiv. To our knowledge, the only other example of such a species showing approximate three-fold symmetry akin to 6a and 6b is a vanadium hydrazine complex supported by a tris(thiolate)amine ligand xxv…”

“…Hydrazine adducts with an η 1 -binding mode to 5-coordinate metal complexes are uncommon. iv , xix , xx , xxi , xxii , xxiii , xxiv To our knowledge, the only other example of such a species showing approximate three-fold symmetry akin to 6a and 6b is a vanadium hydrazine complex supported by a tris(thiolate)amine ligand. xxv …”

Metal-ion directed synthesis of binuclear octaazamacrocyclic complexes of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) and their physico-chemical studies

“…A strong band observed in the region 3210-3260 cm )1 , may be assigned to the coordinated secondary amino stretching modes [30]. All the complexes show sharp bands corresponding to m(C-H), d(C-H) and the phenyl ring vibrations which appear at their expected positions [31]. All the complexes exhibit a strong absorption band in 420-450 cm )1 region assignable to m(M-N) vibration [25].…”