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Variable Coordination of Carbazolyl-Bis(tetrazole) Ligands in Lanthanide Chemistry

Variable Coordination of Carbazolyl-Bis(tetrazole) Ligands in Lanthanide Chemistry

Leah Gajecki, David J Berg, Josh Hoenisch, Allen G Oliver

Dalton Trans. 2018 Nov 21;47(43):15487-15496.

PMID: 30334555

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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP37500951	3,6-Di-tert-butylcarbazole		37500-95-1	Price

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