Trimethylaluminum and borane complexes of primary amines

Autor: Balázs Németh, Jean-Claude Guillemin, Tamás Veszprémi, Jean Paul Guegan
Přispěvatelé: Budapest University of Technology and Economics [Budapest] (BME), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Department of Inorganic and Analytical Chemistry, Hungarian Scientific Research Foundation (OTKA) [K76806], New Szechenyi Plan [TAMOP-4.2.2/B-10/1-2010-0009], PHC Balaton project [24459WC], French Government organized in Hungary, French Institute in Budapest, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Jazyk: angličtina
Rok vydání: 2013
Předmět:
Zdroj: Inorganic Chemistry
Inorganic Chemistry, American Chemical Society, 2013, 52 (1), pp.346-54. ⟨10.1021/ic302091t⟩
Inorganic Chemistry, 2013, 52 (1), pp.346-54. ⟨10.1021/ic302091t⟩
ISSN: 0020-1669
1520-510X
DOI: 10.1021/ic302091t⟩
Popis: International audience; Trimethylaluminum (TMA) complexes of methyl-, n-propyl-, cyclopropyl-, allyl-, and propargylamine were synthesized and their experimental properties and theoretical characteristics were compared with the respective amine-borane analogues. The amine ligand of an amine-TMA Lewis acid-base complex can be easily changed by another amine through a 2:1 amine-TMA intermediate in pentane at room temperature. The exchange of the same ligands in the case of amine-boranes requires remarkably more time in line with the calculated relative energy of the respective transition state. The (1)H and (13)C NMR experiments examining the addition of one or more equivalent of amine to the respective Lewis acid-base complex conclude in the fast exchange of the amine ligand in the NMR time scale only in the cases of amine-TMA complexes, which could also be caused by similar 2:1 complexes. However, in gas phase, only 1:1 amine-TMA complexes are present as evidenced by ultraviolet photoelectron spectroscopy (UPS). The observed UP spectra, which are the first recorded photoelectron spectra of primary amine-TMA compounds, indicate that the stabilization effect of the lone electron pair of nitrogen atom in amines during the borane complexation is stronger than that of the TMA complexation. In line with this observation, the destabilization of the σ(Al-C) orbitals is lower than that of σ(B-H) orbitals during the formation of amine-TMA and amine-borane complexes, respectively. As showed by theoretical calculations, the CH(4) elimination of the studied amine-TMA complexes is exothermic, indicating the possibility of using these compounds in metal organic chemical vapor deposition techniques (MOCVD). On the other hand, our experimental conditions avoid this methane elimination and constitutes the first procedure employing distillation to isolate primary amine-TMA complexes.
Databáze: OpenAIRE
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