Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine.

The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)FeI] (). Molecular structure of was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex at room temperature and the magnetic behavior of in the temperature range of 2-300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively.

Synthesis and Structure of Iron (II) Complexes of Functionalized 1,5-Diaza-3,7-Diphosphacyclooctanes.

In order to synthesize new iron (II) complexes of 1,5-diaza-3,7-diphosphacyclooctanes with a wider variety of the substituents on ligands heteroatoms (including functionalized ones, namely, pyridyl groups) and co-ligands, it was found that these ligands with relatively small phenyl, benzyl, and pyridin-2-yl substituents on phosphorus atoms in acetonitrile formed bis-P,P-chelate -complexes [LFe(CHCN)] (BF), whereas P-mesityl-substituted ligand formed only monoligand P,P-complex [LFe(CHCN)] (BF). 3,7-dibenzyl-1,5-di(1'-()-phenylethyl)-1,5-diaza-3,7-diphosphacyclooctane reacted with hexahydrate of iron (II) tetrafluoroborate in acetone to give an unusual bis-ligand cationic complex of the composition [LFe(BF)] BF, where two fluorine atoms of the tetrafluoroborate unit occupied two pseudo-equatorial positions at roughly octahedral iron ion, according to X-ray diffraction data. 1,5-diaza-3,7-diphosphacyclooctanes replaced tetrahydrofurane and one of the carbonyl ligands of cyclopentadienyldicarbonyl(tetrahydrofuran)iron (II) tetrafluoroborate to form heteroligand complexes [CpFeL(CO)]BF.

First iron and cobalt(II) hexabromoclathrochelates: structural, magnetic, redox, and electrocatalytic behavior.

Template condensation of dibromoglyoxime with n-butylboronic acid on the corresponding metal ion as a matrix under vigorous reaction conditions afforded iron and cobalt(ii) hexabromoclathrochelates. The paramagnetic cobalt clathrochelate was found to be a low-spin complex at temperatures below 100 K, with a gradual increase in the effective magnetic moment at higher temperatures due to the temperature 1/2↔3/2 spin crossover and a gap caused by the structure phase transition. The multitemperature X-ray and DSC studies of this complex and its iron(ii)-containing analog also showed temperature structural transitions.

N,N'-fused bisphosphole: heteroaromatic molecule with two-coordinate and formally divalent phosphorus. Synthesis, electronic structure, and chemical properties.

The reduction of 6,12-dichloro-1,2,3,4,7,8,9,10-octahydro-6H,12H-[1,2,3]benzodiazaphospholo[2,1-a][1,2,3]benzodiazaphosphole (3) by metallic magnesium in tetrahydrofuran (THF) affords the N,N'-fused bisphosphole 1 in 92% yield. The compound reveals a novel type of 10π-electron heteroaromatic system [NICS(0) = -11.4], containing a two-coordinate and formally divalent phosphorus atom.