Do trinuclear triplesalen complexes exhibit cooperative effects? Synthesis, characterization, and enantioselective catalytic sulfoxidation by chiral trinuclear Fe(III) triplesalen complexes

Chemistry : a European Journal
Chandan MukherjeeThorsten Glaser

Abstract

The chiral triplesalen ligand H(6)chand provides three chiral salen ligand compartments in a meta-phenylene arrangement by a phloroglucinol backbone. The two diastereomeric versions H(6)chand(RR) and H(6)chand(rac) have been used to synthesize the enantiomerically pure chiral complex [(FeCl)(3)(chand(RR))] (3(RR)) and the racemic complex [(FeCl)(3)(chand(rac))] (3(rac)). The molecular structure of the free ligand H(6)chand(rac) exhibits at the terminal donor sides the O-protonated phenol-imine tautomer and at the central donor sides the N-protonated keto-enamine tautomer. The trinuclear complexes are comprised of five-coordinate square-pyramidal Fe(III) ions with a chloride at the axial positions. The crystal structure of 3(rac) exhibits collinear chiral channels of approximately 11 A in diameter making up 33.6 % of the volume of the crystals, whereas the crystal structure of 3(RR) exhibits voids of 560 A(3). Mössbauer spectroscopy demonstrates the presence of Fe(III) high-spin ions. UV/Vis spectroscopy is in accordance with a large delocalized system in the central backbone evidenced by strong low-energy shifts of the imine pi-pi* transitions relative to that of the terminal units. Magnetic measurements reveal weak intramolecu...Continue Reading

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Citations

Sep 24, 2010·Chemical Communications : Chem Comm·Thorsten Glaser
May 12, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Tim J DunnTim Storr
Jan 25, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Bastian FeldscherThorsten Glaser
Apr 12, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Ryan M Clarke, Tim Storr
Jun 12, 2013·Chemistry : a European Journal·Tim J DunnTim Storr
Jan 23, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Samir Ghorai, Chandan Mukherjee
Sep 10, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Peter Happ, Eva Rentschler
May 20, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Chandan MukherjeeThorsten Glaser
Jan 10, 2012·The Journal of Organic Chemistry·Carl-Georg Freiherr von RichthofenThorsten Glaser

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