Universität zu Köln

Czympiel, Lisa, Pfrommer, Johannes, Tyrra, Wieland, Schaefer, Mathias and Mathur, Sanjay (2015). Ligand-Modulated Chemical and Structural Implications in Four-, Five-, and Six-fold Coordinated Aluminum Heteroaryl Alkenolates. Inorg. Chem., 54 (1). S. 25 - 38. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-510X

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Abstract

Synthesis and characterization (gas phase, solution, and solid-state) of a series of four-, five- and six-fold coordinated heteroaryl-alkenolato aluminum complexes were performed to demonstrate the delicate interplay of structural and chemical influences of ligands in the design of new precursors for chemical vapor deposition. We are investigating the properties of heteroaryl alkenols as O<^>N chelating ligands [where O<^>N is 3,3,3-trifluoro(pyridin-2-yl)propen-2-ol (H-PyTFP), 3,3,3-trifluoro(1,3-benzimidazol-2-yl)propen-2-ol (H-BITFP), 3,3,3-trifluoro(dimethyl-1,3-oxazol-2-yl)propen-2-ol (H-DMOTFP), 3,3,3-trifluoro(1,3-benzoxazol-2-yl)propen-2-ol (H-BOTFP), 3,3,3-trifluoro(1,3-benzthiazol-2-yl)propen-2-ol (H-BTTFP), and 3,3,3-trifluoro(dimethyl-1,3-thiazol-2-yl)propen-2-ol (H-DMTTFP)] to prepare volatile and air-stable compounds. All three methyl groups in highly reactive AlMe3 could be replaced by H-PyTFP, H-BITFP, H-DMOTFP, and H-BOTFP yielding octahedral complexes of the type Al(O<^>N)(3); under similar conditions H-BTTFP and H-DMTTFP produced heteroleptic MeAl(O<^>N)(2) compounds with five-fold coordinated aluminum centers. Various attempts to obtain tris-alkenolato derivatives by choosing higher temperatures and prolonged reaction times were not successful. The reaction of H-PyTFP with [Al(OtBu)(3)](2) produced the dimeric heteroleptic [Al(PyTFP)(OtBu)(2)](2) complex with Al atoms present in both octahedral (Oh) and tetrahedral (Td) coordination in a single molecular unit. The introduction of the chelating ligand H-PyTFP in the dimeric framework of [Al(OtBu)(3)](2) enhanced the stability against hydrolyses significantly. The tendency of Al(III) centers to preferably coordinate in Td or Oh environment was elucidated by hydrolysis studies of monomeric Al(PyTFP)(3), Al(BOTFP)(3), and MeAl(BTTFP)(2) that produced hydroxo-bridged dimers to retain the octahedral environment for Al atoms. Surprisingly, hydrolysis of monomeric MeAl(DMTTFP)(2) yielded an oxo-bridged dimer with two five-fold coordinated aluminum centers. The structural features of all new complexes were investigated in solution, vapor, and solid state by multinuclear NMR spectroscopy, EI-MS spectrometry, and single-crystal X-ray diffraction analyses, respectively.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Czympiel, Lisa UNSPECIFIED UNSPECIFIED UNSPECIFIED Pfrommer, Johannes UNSPECIFIED UNSPECIFIED UNSPECIFIED Tyrra, Wieland UNSPECIFIED UNSPECIFIED UNSPECIFIED Schaefer, Mathias UNSPECIFIED UNSPECIFIED UNSPECIFIED Mathur, Sanjay UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-414791
DOI:	10.1021/ic502549m
Journal or Publication Title:	Inorg. Chem.
Volume:	54
Number:	1
Page Range:	S. 25 - 38
Date:	2015
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1520-510X
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language BETA-DIKETIMINATO LIGANDS; AL-27 NMR-SPECTROSCOPY; PRECURSOR CHEMISTRY; THIN-FILMS; CRYSTAL-STRUCTURES; VAPOR-DEPOSITION; DIKETONATE COMPLEXES; MOLECULAR-STRUCTURE; OPTICAL-PROPERTIES; FACILE SYNTHESES Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/41479