MSP 28P Crystal structure of decanuclear Mn(III) complexes based on S-methyl-isotiosemicarbazone ligands
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BOUROSH, Pavlina, PALAMARCIUC, Oleg, CLERAC, Rodolphe, KRAVTSOV, Victor, REVENKO, M.. MSP 28P Crystal structure of decanuclear Mn(III) complexes based on S-methyl-isotiosemicarbazone ligands. In: Materials Science and Condensed Matter Physics, 13-17 septembrie 2010, Chișinău. Chișinău, Republica Moldova: Institutul de Fizică Aplicată, 2010, Editia 5, p. 96.
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Materials Science and Condensed Matter Physics
Editia 5, 2010
Conferința "Materials Science and Condensed Matter Physics"
Chișinău, Moldova, 13-17 septembrie 2010

MSP 28P Crystal structure of decanuclear Mn(III) complexes based on S-methyl-isotiosemicarbazone ligands


Pag. 96-96

Bourosh Pavlina1, Palamarciuc Oleg234, Clerac Rodolphe43, Kravtsov Victor1, Revenko M.2
 
1 Institute of Applied Physics,
2 Moldova State University,
3 Centrul de Cercetări „Paul Pascal”, CRPP-CNRS, Pessac,
4 University of Bordeaux
 
Disponibil în IBN: 15 aprilie 2021


Rezumat

Manganese chemistry continues to be a rich source of cluster complexes with a variety of metal nuclearities mostly represented by Mn carboxylate clusters. As part of our a continuing interest in the structural and magnetic properties of Mn clusters as well as in cluster based polymers, we have been seeking to for new examples of such species based on non carboxylate ligands. Manganesse(II) is little-known as templating ion for condensation S-methyl-isothiosemicarbazide [1, 2]. Nevertheless using Mn(II) precursors, we have successfully synthesize and structurally characterize three novel decanuclear manganese(III) complexes all comprising [Mn10O6]18+ core. Peripheral ligation is provided by two tridentate (L1) and four pentadentate (L2) ligands on the base S-methyl-isothiosemicarbazide and bridging function of two deprotonated and two neutral ethanol molecules. The composition of Mn(III) complexes very similar and differs only substituent in salyciliden fragment (R=H in 1, 2 and R=Br in 3) and solvent molecules (CH3OH, C2H5OH, (C2H5)2O, H2O). The crystal structure of these cluster complexes has been studied by single crystal X-ray method : 1 P`1, a=14.165(3) Å, b=14.481(3) Å, c=15.382(3) Å, a=91.32(3)°, β=109.635(3)°, g=99.491(3)°, Z=1, R=0.0437, 2 P21/c, a=15.801(3) Å, b=21.304(4) Å, c=17.151(3) Å, β=110.05(3)°, Z=2, R=0.0466 and 3 P`1, a=14.9523(8) Å, b=16.0687(7) Å, c=16.4935(9) Å, a=109.526(3)°, β=92.988(3)°, g=110.421(3)°, Z=1, R=0.0655.figureThe general formula of Mn(III) complexes in 1 – 3 is [Mn10O6L1 2L2 4(OC2H5)2(OHC2H5)n], were n equals to 4 in 1, 3, and 2 in 2. Template condensation of L1 with 2-formylpyridine in the presence of metal resulted in L2 formation and redox Mn(II)®Mn(III) transformation. The manganese(III) ions have different coordination polyhedra: in 2 – six metal ions have square-pyramidal and only four distorted octahedral surrounding, in 1, 3 six metal ions have distorted octahedral surrounding due to two additional monodentate ethanol molecules coordinated to unsaturated outer Mn ions.