Synthese, Röntgenstrukturanalyse und Multikern-NMR-spektroskopische Untersuchung einiger intramolekular stickstoffstabilisierter Bor-, Aluminium- und Galliumorganyle

Abstract

Die intramolekular stickstoffstabilisierten Organoaluminium‐ und Organoborverbindungen Me2Al‐ (CH2)3NMe2 (1), Me2AlC10H6‐8‐NMe2 (2), iPr2Al(CH2)3NEt2 (3), (CH2)5Al(CH2)3NMe2 (4) und (CH2)5B(CH2)3NMe2 (5) werden aus Me2AlCl und den entsprechenden Lithiumorganylen bzw. aus AlCl3 oder BCl3, dem Lithiumalkyl und iPrMgCl oder BrMg(CH2)5MgBr erhalten. AlCl3 und GaCl3 reagieren mit LiCH2CHMeCH2NMe2 bzw. Li(CH2)3NMe2 unter Bildung von Cl2AlCH2CHMeCH2NMe2 (6) bzw. Cl2Al(CH2)3NMe2 (8) und Cl2Ga(CH2)3NMe2 (9). Bei der Umsetzung von 6 bzw. 8 oder 9 mit BrMg(CH2)5MgBr bzw. BrMg(CH2)6MgBr entstehen (CH2)5AlCH2CHMeCH2NMe2 (7) bzw. (CH2)6Al(CH2)3NMe2 (10) und (CH2)6Ga(CH2)3NMe2 (11). Das durch Komproportionierung aus AlCl3 und Me2AlCl erhaltene MeAlCl2 reagiert mit 2 Äquivalenten Li(CH2)3NMe2 zu MeAl[(CH2)3NMe2]2 (12) und mit MeN[(CH2)3MgCl]2 unter Bildung von MeAl[(CH2)3]2NMe (13). Entsprechend reagieren MeAlCl2 oder MeGaCl2 bzw. GaCl3 mit einem Äquivalent Lithiumorganyl zu den intramolekular stickstoffstabilisierten Organoaluminium‐ und Organogalliumchloriden MeClAl(CH2)3NMe2 (14), MeClGa(CH2)3NMe2 (15), MeClGaC6H4‐2‐CH2NMe2 (16) und Cl2GaC6H4‐2‐CHMeNMe2 (17). Die Verbindungen wurden durch Elementaranalysen, 1H‐, 11B‐, 13C‐ und 27Al‐NMR‐Untersuchungen sowie massenspektrometrisch charakterisiert. Die Einkristall‐Röntgenstrukturanalysen von 1, 2, 4, 5 und 17 zeigen die monomeren Molekülstrukturen mit intramolekularer Stickstoff‐Koordination.

Unearthing [3‐(Dimethylamino)propyl]aluminium(III) Complexes as Novel Atomic Layer Deposition (ALD) Precursors for Al2O3: Synthesis, Characterization and ALD Process Development

“…Although [3‐(dimethylamino)propyl]dimethylaluminium, [AlMe 2 (DMP)] (DMAD), was suggested by Schumann et al. as a potential precursor for chemical vapor deposition (CVD) applications, there are no reports in the literature about its usage in CVD or ALD . In this compound, the 3‐(dimethylamino)propyl (DMP) ligand stabilizes the Al center by donating electrons through the free electron pair of the amine nitrogen, resulting in a chelating complex.…”

“…The synthesis of the new Al compounds was initiated with [3‐(dimethylamino)propyl]aluminium dichloride [AlCl 2 (DMP)], which reacts in a transmetalation reaction with the corresponding lithium dialkylamide to yield the desired product. For compounds 2 and 3 , the lithium dialkylamide was produced in situ by reaction of the corresponding alkylamine with butyl lithium, while the commercially available lithium dimethyl amide was used for synthesis of compound 1 (Scheme ).…”

Inherent Stability Limits of Intramolecular Boron Nitrogen Lewis Acid–Base Pairs

“…This can be interpreted as a strong dative bond, especially considering the ring strain of the five‐membered ring system. Due to the increase of Lewis acidity of the boron atom by C 6 F 5 substituents, the BN bond lengths in these compounds are shorter compared to the known related ring system [9‐(2‐dimethylaminomethyl)phenyl]‐9‐borabicyclo[3.3.1]nonane (1.746(3) Å)20 and similar to (CH 2 ) 5 B(CH 2 ) 3 NMe 2 (1.682(4) Å)21 The BN bond lengths in compounds 5 – 7 are nearly the same as in the comparable five‐membered BC 3 N ring of (C 6 F 5 ) 2 BC 6 H 4 (Me)NMe 2 with 1.666(3) Å 22…”

Palladium-Catalyzed Cross-Methylation of Haloarenes Possessing Active Hydrogen Atoms by Intramolecularly Stabilized Dimethylindium and Dimethylaluminum Reagents

“…IR spectra were recorded on a Bruker model Vector 22 FTIR instrument, and HPLC separations were performed on a Jasco TRI-ROTAR IV machine equipped with a DG-3510 degasser and UVIDEC 100-VI UV spectrophotometer. Trimethylindium, [16] trin-butylindium, [16] [3-(dimethylamino)propyl-C,N]dimethylaluminum (1a), [17] [3-(dimethylamino)propyl-C,N]dimethylgallium (1b), [18] [3-(dimethylamino)propyl-C,N]dimethylindium (1c), [18] bis{µ-[2-(dimethylamino)ethanolato-N,O:O]}tetramethyldi-aluminum (2a), [19] bis{µ- [2-(dimethylamino)ethanolato-N,O:O]}-tetramethyldigallium (2b), [20] and bis{µ-[2-(dimethylamino)ethanolato-N,O:O]}tetramethyldiindium (2c) [21] were prepared as described in the literature. 4-Hydroxyphenyl trifluoromethanesulfonate was synthesized from 4-aminophenol via the diazonium tetrafluoroborate.…”