Universität zu Köln

Tutacz, Peter, Harmgarth, Nicole, Zoerner, Florian, Liebing, Phil, Hilfert, Liane, Engelhardt, Felix, Busse, Sabine and Edelmann, Frank T. (2018). Two Series of New Volatile Rare-Earth Metal Tris(guanidinates) and Tris(amidinates). Z. Anorg. Allg. Chem., 644 (23). S. 1653 - 1660. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3749

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Abstract

Two series of new volatile, homoleptic lanthanide(III) tris(guanidinate) and tris(amidinate) complexes were synthesized and fully characterized. Treatment of anhydrous rare-earth metal(III) chlorides, LnCl(3), with three equiv. of the aziridine-derived lithium guanidinate Li[c-C2H4NC(NiPr)(2)] (3) afforded the new homoleptic tris(guanidinate) complexes [c-C2H4NC(NiPr)(2)](3)Ln (4) (Ln = Sc, Pr, Nd, Sm, Eu, Ho, Tm) in good yields (68-80 %). In a similar manner, the homoleptic tris(amidinate) complexes [iPrC(NiPr)(2)](3)Ln (6) Ln = Sc, Ce, Pr, Nd, Tb, Dy, Er, Yb) were prepared from LnCl(3) and the all-isopropyl-substituted lithium amidinate Li[iPrC(NiPr)(2)] (5) in a molar ratio of 1:3. Variable-temperature H-1 NMR studies of the paramagnetic derivatives 4Pr-4Tm revealed Curie-type behavior. H-1 NMR spectroscopic data of complexes 6 indicated severe steric crowding due to the presence of nine isopropyl groups in these molecules. The molecular and crystal structures of eight title compounds (4Sc, 4Pr, 4Nd, 4Sm, 4Eu, 4Ho, 4Tm, and 6Er) were determined through single-crystal X-ray diffraction studies. All complexes 4 exhibit similar molecular structures, comprising distorted octahedral molecular structures with small bite angles. Sublimation temperatures of 4 at 0.05 mbar were determined to be in the range between 151 degrees C (4Eu) and 194 degrees C (4Tm), whereas the complexes 6 sublime in the temperature range between 140 degrees C (6Sc) and 180 degrees C (6Ce), so that the use of these precursors in future ALD or CVD studies appears feasible.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Tutacz, Peter UNSPECIFIED UNSPECIFIED UNSPECIFIED Harmgarth, Nicole UNSPECIFIED UNSPECIFIED UNSPECIFIED Zoerner, Florian UNSPECIFIED UNSPECIFIED UNSPECIFIED Liebing, Phil UNSPECIFIED UNSPECIFIED UNSPECIFIED Hilfert, Liane UNSPECIFIED UNSPECIFIED UNSPECIFIED Engelhardt, Felix UNSPECIFIED UNSPECIFIED UNSPECIFIED Busse, Sabine UNSPECIFIED UNSPECIFIED UNSPECIFIED Edelmann, Frank T. UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-162142
DOI:	10.1002/zaac.201800393
Journal or Publication Title:	Z. Anorg. Allg. Chem.
Volume:	644
Number:	23
Page Range:	S. 1653 - 1660
Date:	2018
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1521-3749
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language ATOMIC-LAYER DEPOSITION; LANTHANIDE COMPLEXES; PRECURSORS; AMIDINATE; LIGANDS; MOCVD; GUANIDINATE; CHEMISTRY; FILMS; ALD Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/16214