Variable coordination of carbazolyl-bis(tetrazole) ligands in lanthanide chemistry??

Dalton Transactions Pub Date: 2018-10-12 DOI: 10.1039/C8DT02757A

Abstract

The synthesis of the protioligand 1,8-bis(2′-isopropyltetrazo-5′-yl)-3,6-di-tert-butylcarbazole, HCzTiPr2, is described. The acid–base reaction of 2 with various Ln[N(SiMe3)2]3 (Ln = Ce, Sm, Er, Yb, Y) precursors leads to products displaying a variety of different bonding modes for the CzTiPr? ligand as revealed by X-ray crystallographic studies. The smaller lanthanides form Ln(CzTiPr)[N(SiMe3)2]2 complexes (Ln = Er (3), Yb(4)) with a near planar, tridentate coordination mode for the CzTiPr? ligand. In contrast, the larger lanthanides form Ln(CzTiPr)2[N(SiMe3)2] complexes (Ln = Ce (5), Sm (6)) at room temperature that feature a sandwich structure with a highly distorted tridentate mode where tetrazole canting allows the metal to sit well out of the carbazole plane. Attempts to force additional CzTiPr? ligands onto Er or Yb at elevated temperature results in isolation of trace siloxide complexes Ln(CzTiPr)2(OSiMe3) (Ln = Er (3a), Yb (4a)) that adopt a flat tridentate ligand bonding mode similar to 3 and 4. Surprisingly, the high temperature reaction of 2 with Y[N(SiMe3)2]3 affords Y(CzTiPr)3, 7, featuring two tridentate and one bidentate CzTiPr ligands. Partial hydrolysis of 6 occurs over time to produce a hydroxo-bridged dimer that also features one bridging and one bidentate CzTiPr ligand, Sm(κ3-CzTiPr)(κ3-μ-CzTiPr)(μ-OH)2Sm(κ3-CzTiPr)(κ2-CzTiPr), 6a, further illustrating the remarkable coordinative flexibility of the CzTiPr ligand system.

Graphical abstract: Variable coordination of carbazolyl-bis(tetrazole) ligands in lanthanide chemistry
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