Synthesis and characterization of iron and cobalt clathrochelate complexes derived from oxime-hydrazone ligands

Tris‐Dioximate Cobalt(I,II,III) Clathrochelates: Stabilization of Different Oxidation and Spin States of an Encapsulated Metal Ion by Ribbed Functionalization

“…both the cobalt(II) and cobalt(III) complexes were isolated preparatively. [19] The redox characteristics of both the Co +/2+ and Co 2+/3+ couples for such complexes are very similar to those of the cobalt clathrochelates with electrondonating substituents.…”

“…The signal corresponding to the apical fluorine substituents in the 19 F NMR spectrum of this clathrochelate was found at δ = -60.7 ppm. The comparison of this value with those for the low-spin cobalt(II) complexes CoDm 2 Bd-(BF) 2 and CoBd 2 Dm(BF) 2 (where Dm 2-and Bd 2-are dimethylglyoxime and α-benzyldioxime dianions, δ19 F = -111.6 and -110.1 ppm, respectively [11] ) and that for their diamagnetic iron(II) analogue [12] (δ19 F = -90.5 ppm) demonstrated the opposite direction of the paramagnetic shift of the 19 F NMR signal for the complex Co(Cl 2 Gm) 3 (BF) 2 . Such a dramatic change could occur only due to the preferential population of the high-spin state of this complex in solution at room temperature.…”

Synthesis and structure of the ferrocenylboron-capped clathrochelate iron(ii) oximehydrazonates

“…[1][2][3][4][5][6][7][8][9] In particular, the synthesis of the iron(II) and cobalt(II) semiclathroche lates with the apical ferrocenyl substituents has earlier been reported. The following condensation of these semi сlathrochelates with an aqueous solution of formalde hyde afforded the clathrochelates with 1,3,5 triazacyclo hexane ring as an apical substituent.…”

“…The following condensation of these semi сlathrochelates with an aqueous solution of formalde hyde afforded the clathrochelates with 1,3,5 triazacyclo hexane ring as an apical substituent. 8, 9 However, the pro cedures described have several disadvantages, such as the use of an aqueous solution of formaldehyde for macrocy clization, which causes the side hydrolysis reactions. In addition, the clathrochelates synthesized 8, 9 are poorly soluble in organic solvents.…”

“…8, 9 However, the pro cedures described have several disadvantages, such as the use of an aqueous solution of formaldehyde for macrocy clization, which causes the side hydrolysis reactions. In addition, the clathrochelates synthesized 8, 9 are poorly soluble in organic solvents.…”