The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(III) ions

Imran M, Neumann B, Stammler H-G, Monkowius U, Ertl M, Mitzel NW (2013)
Dalton Transactions 42(44): 15785-15795.

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Abstract
Alkali metal salts of a novel Janus scorpionate ligand [(Tr-Me)](-) with hard and soft donor sites (N, S) were synthesized by the reaction of 3-mercapto-4-methyl-1,2,4-triazole (L) with NaBH4 and KBH4, respectively, via Trofimenko's protocol. The resulting compounds were the sodium and potassium complexes [Na(Tr-Me)] (1), [K(Tr-Me)] (2) and the mixed ion compound [KNa(Tr-Me)] (3). [K(Tr-Me)] (2) was reacted with bismuth(III) chloride to afford the complexes [Bi(Tr-Me)(Cl)(mu-Cl)(2)](2) (5) and [Bi(Tr-Me)(Cl)(2)(mu-Cl)](n) (6). Compound 5 was formed when 2 was applied to BiCl3 in a molar ratio 2:1, while 6 was achieved when a ratio of 1:1 was used. The reaction of 3-mercapto-4-methyl-1,2,4-triazole (L) with BiCl3 led to the formation of the complex [Bi(L) 4(Cl) 2] Cl (7). The products were characterized by NMR and IR spectroscopy, elemental analyses and mass spectrometry. Solid state structures were determined by X-ray diffraction of single crystals of 1, 3, 3a, 5, 6 and 7. The alkali metal scorpionates 1-3 are coordination polymers with alternating orientation of the ligands. They dissociate in solution as observed in NMR measurements. Negative mode ESI-MS data also indicate the presence of monomers. The bismuth complex 5 is dimeric and 6 is polymeric, and both are bridged via chloro ligands. The three bismuth complexes 5, 6 and 7 have highly distorted octahedral coordination geometries. The influence of the stereochemically active lone pair was found to be most pronounced in the dimeric complex 5. The ligand Tr-Me and all bismuth complexes were also screened for their photo-luminescence activity. Whereas solutions of Tr-Me exhibit no luminescence, 7 is only emissive at 77 K, and 5 is emissive both at r.t. and 77 K.
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Imran M, Neumann B, Stammler H-G, Monkowius U, Ertl M, Mitzel NW. The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(III) ions. Dalton Transactions. 2013;42(44):15785-15795.
Imran, M., Neumann, B., Stammler, H. - G., Monkowius, U., Ertl, M., & Mitzel, N. W. (2013). The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(III) ions. Dalton Transactions, 42(44), 15785-15795.
Imran, M., Neumann, B., Stammler, H. - G., Monkowius, U., Ertl, M., and Mitzel, N. W. (2013). The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(III) ions. Dalton Transactions 42, 15785-15795.
Imran, M., et al., 2013. The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(III) ions. Dalton Transactions, 42(44), p 15785-15795.
M. Imran, et al., “The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(III) ions”, Dalton Transactions, vol. 42, 2013, pp. 15785-15795.
Imran, M., Neumann, B., Stammler, H.-G., Monkowius, U., Ertl, M., Mitzel, N.W.: The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(III) ions. Dalton Transactions. 42, 15785-15795 (2013).
Imran, Muhammad, Neumann, Beate, Stammler, Hans-Georg, Monkowius, Uwe, Ertl, Martin, and Mitzel, Norbert W. “The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(III) ions”. Dalton Transactions 42.44 (2013): 15785-15795.
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