Monomeric thorium chalcogenolates with bipyridine and terpyridine ligands

TY - JOUR

T1 - Monomeric thorium chalcogenolates with bipyridine and terpyridine ligands

AU - Ringgold, Marissa

AU - Wu, Wen

AU - Stuber, Matthew

AU - Kornienko, Anna Y.

AU - Emge, Thomas

AU - Brennan, John G.

N1 - Publisher Copyright: © 2018 The Royal Society of Chemistry.

PY - 2018

Y1 - 2018

N2 - Thorium chalcogenolates Th(ER)4 react with 2,2′-bipyridine (bipy) to form complexes with the stoichiometry (bipy)2Th(ER)4 (E = S, Se; R = Ph, C6F5). All four compounds have been isolated and characterized by spectroscopic methods and low-temperature single crystal X-ray diffraction. Two of the products, (bipy)2Th(SC6F5)4 and (bipy)2Th(SeC6F5)4, crystallize with lattice solvent, (bipy)2Th(SPh)4 crystallizes with no lattice solvent, and the selenolate (bipy)2Th(SePh)4 crystallizes in two phases, with and without lattice solvent. In all four compounds the available volume for coordination bounded by the two bipy ligands is large enough to allow significant conformational flexibility of thiolate or selenolate ligands. 77Se NMR confirms that the structures of the selenolate products are the same in pyridine solution and in the solid state. Attempts to prepare analogous derivatives with 2,2′,6′,2′′-terpyridine (terpy) were successful only in the isolation of (terpy)(py)Th(SPh)4, the first terpy compound of thorium. These materials are thermochromic, with color attributed to ligand-to-ligand charge transfer excitations.

AB - Thorium chalcogenolates Th(ER)4 react with 2,2′-bipyridine (bipy) to form complexes with the stoichiometry (bipy)2Th(ER)4 (E = S, Se; R = Ph, C6F5). All four compounds have been isolated and characterized by spectroscopic methods and low-temperature single crystal X-ray diffraction. Two of the products, (bipy)2Th(SC6F5)4 and (bipy)2Th(SeC6F5)4, crystallize with lattice solvent, (bipy)2Th(SPh)4 crystallizes with no lattice solvent, and the selenolate (bipy)2Th(SePh)4 crystallizes in two phases, with and without lattice solvent. In all four compounds the available volume for coordination bounded by the two bipy ligands is large enough to allow significant conformational flexibility of thiolate or selenolate ligands. 77Se NMR confirms that the structures of the selenolate products are the same in pyridine solution and in the solid state. Attempts to prepare analogous derivatives with 2,2′,6′,2′′-terpyridine (terpy) were successful only in the isolation of (terpy)(py)Th(SPh)4, the first terpy compound of thorium. These materials are thermochromic, with color attributed to ligand-to-ligand charge transfer excitations.

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U2 - 10.1039/c8dt02543f

DO - 10.1039/c8dt02543f

M3 - Article

C2 - 30277236

SN - 1477-9226

VL - 47

SP - 14652

EP - 14661

JO - Dalton Transactions

JF - Dalton Transactions

IS - 41

ER -