Combined charge and spin density experimental study of the yttrium(III) semiquinonato complex Y(HBPz3)2(DTBSQ) and DFT calculations

High-resolution X-ray diffraction and polarized neutron diffraction experiments have been performed on the Y-semiquinonate complex, Y(HBPz3)2(DTBSQ), in order to determine the charge and spin densities in the paramagnetic ground state, S = (1/2). The aim of these combined studies is to bring new insights to the antiferromagnetic coupling mechanism between the semiquinonate radical and the rare earth ion in the isomorphous Gd(HBPz3)2(DTBSQ) complex. The experimental charge density at 106 K yields detailed information about the bonding between the Y3+ ion and the semiquinonate ligand; the topological charge of the yttrium atom indicates a transfer of about 1.5 electrons from the radical toward the Y3+ ion in the complex, in agreement with DFT calculations. The electron density deformation map reveals well-resolved oxygen lone pairs with one lobe polarized toward the yttrium atom. The determination of the induced spin density at 1.9 K under an applied magnetic field of 9.5 T permits the visualization of the delocalized magnetic orbital of the radical throughout the entire molecule. The spin is mainly distributed on the oxygen atoms [O1 (0.12(1) mu B), O2(0.11(1) mu B)] and the carbon atoms [C21 (0.24(1) mu B), C22(0.20(1) mu B), C24(0.16(1) mu B), C25(0.12(1) mu B)] of the carbonyl ring. A significant spin delocalization on the yttrium site of 0.08(2) mu B is observed, proving that a direct overlap with the radical magnetic orbital can occur at the rare earth site and lead to antiferromagnetic coupling. The DFT calculations are in good quantitative agreement with the experimental charge density results, but they underestimate the spin delocalization of the oxygen toward the yttrium and the carbon atoms of the carbonyl ring.     

X-ray crystallographic investigation of the adduct of 1-demethylamino-2-(4-bromophenyl-2H-isoindole with N-phenylmalemide

An unusual path for the reaction of 2-aryl-1-dimethylamino-2H-isoindoles with N-R-maleimides, leading to the imides of l,2-dihydronaphthalene-2,3-dicarboxylic adds, was established by x-ray crystallographic analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 614–618, May, 1992     

Reaction of ethyl perfluoromethacrylate with [η5-C5H5Fe(CO)2]− anion

Conclusions The cis-trans isomers of the vinylic fluorine substitution product were isolated and characterized when Na[⁵-C₅H₅Fe(CO)₂] is reacted with ethyl perfluoromethacrylate.Deceased.The authors express their gratitude to E. M. Rokhlin and U. Utebaev for supplying the ethyl perfluoromethacrylate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 705–706, March, 1977.