6533b838fe1ef96bd12a501d

RESEARCH PRODUCT

Synthesis, molecular and electronic structures of a paramagnetic trimetallic cluster containing an unusual Mo3(μ3-Se)2(μ-Se)3 core

Alexander V. VirovetsRosa LlusarCarlos J. Gómez-garcíaMaxim R. RyzhikovSergey N. KonchenkoPavel A. Petrov

subject

MolybdenumCrystal structureCrystal structurelaw.inventionInorganic ChemistrySeleniumchemistry.chemical_compoundCrystallographyDelocalized electronParamagnetismUnpaired electronchemistrylawSelenideMaterials ChemistryCluster (physics)Physical and Theoretical ChemistryElectron paramagnetic resonanceGround stateCluster compoundsESR

description

Abstract The electron precise [Mo3(μ3-Se)(μ-Se)3(dppe)3Br3]+ incomplete cuboidal complex, with six cluster skeletal electrons (CSE), was converted into the paramagnetic bicapped [Mo3(μ3-Se)2(μ-Se)3(dppe)3]+ cluster (1+), with an unusual seven metal electron population, by treatment with elemental Ga. The cluster core consists of an almost equilateral Mo3 triangle (Mo–Mo distances are in the range 2.7583(7)–2.7748(7) A with an average value of 2.77(3) A), capped by two selenide ligands. The remaining selenium atoms bridge adjacent metal atoms, defining a virtually planar Mo3(μ-Se)3 unit, with the capping Se atoms positioned above and below this plane. The new complex possesses a doublet ground state with the unpaired electron density delocalized over the three metal atoms. DFT calculations show that the HOMO has “a1” symmetry, precluding any Jahn–Teller distortion on the cluster core and giving support to EPR and structural observations.

yearjournalcountryeditionlanguage
2014-10-01Polyhedron
https://doi.org/10.1016/j.poly.2014.05.038