Journal article

Authors list: Müller-Buschbaum, K; Quitmann, CC

Publication year: 2004

Pages: 4330-4337

Journal: European Journal of Inorganic Chemistry

Volume number: 2004

Issue number: 21

ISSN: 1434-1948

DOI Link: https://doi.org/10.1002/ejic.200400516

Publisher: Wiley-VCH Verlag

Abstract: 
The solvent-free melt reaction of carbazole (CbzH, C12H8NH) with samarium metal yields (1)(infinity)[Sm-2(Cbz)(5)](CbzH) (1), whilst the melt reactions with thulium, neodymium and gadolinium give [Tm-2(Cbz)(6)] (2), [Nd-2(Cbz)(6)] (3) and [Gd-2(Cbz)(6)] (4), respectively. Compounds 1 and 2 were obtained as single crystals and their crystal structures determined by single-crystal X-ray analysis, whilst 3 and 4 were obtained as powders. X-ray powder diffraction studies show that the gadolinium-containing complex 4 is isotypic to the thulium complex 2, whereas the neodymium-containing complex 3 is not. Compound 1 contains alternating Sm-II and Sm-III cations in a chain structure. Complex 2 only exhibits dimeric units of Tm-III. Besides Ln-N coordination, the crystal structures of both compounds show eta(6)-pi interactions with the phenyl rings of the carbazolate ligands. This leads to small coordination polyhedra, such as connected tetrahedra of two nitrogen atoms and two eta(6)-pi-coordinated phenyl rings around Stan, and trigonal bipyramids of five nitrogen atoms around Sm-III for 1, as well as tetrahedra of three nitrogen atoms and one eta(6)-pi-phenyl interaction around Tm-III for 2. From the trend of the E-Ln(II/III) redox potentials, the complexes of neodymium and gadolinium are also trivalent. For 1-4 the results of FIR, MIR and Raman spectroscopy as well as simultaneous DTA/TG analyses are also presented. (C) Wiley-VCH Verlag GmbH Co.

Harvard Citation style: Müller-Buschbaum, K. and Quitmann, C. (2004) Homoleptic rare-earth carbazolates and the trends of their ELnII/III redox potentials: Mixed-valent samarium in (1)(infinity) [Sm-2(CbZ)(5)](CbzH) (CbzH = carbazole) and trivalent thulium, neodymium and gadolinium in [Ln(2)(Cbz)(6)], European Journal of Inorganic Chemistry, 2004(21), pp. 4330-4337. https://doi.org/10.1002/ejic.200400516

APA Citation style: Müller-Buschbaum, K., & Quitmann, C. (2004). Homoleptic rare-earth carbazolates and the trends of their ELnII/III redox potentials: Mixed-valent samarium in (1)(infinity) [Sm-2(CbZ)(5)](CbzH) (CbzH = carbazole) and trivalent thulium, neodymium and gadolinium in [Ln(2)(Cbz)(6)]. European Journal of Inorganic Chemistry. 2004(21), 4330-4337. https://doi.org/10.1002/ejic.200400516