We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Reactions of MAlH<sub>4</sub> (M = Li, Na) with primary amines — Synthetic and structural studies of alkali metal tetrakis(amido)aluminates and related dinuclear complexes.
- Authors
Eisler, Dana J.; Chivers, Tristram
- Abstract
The reactions of MAlH4 (M = Li, Na) with primary amines NH2R (R = t-Bu, i-Pr, p-tolyl) in a 1:4 molar ratio in THF produce the tetrakis(amido)aluminates, <NOBR>[M(THF)n]</NOBR><NOBR>[Al(NHR)4],</NOBR> in yields of 46%–82% together with secondary products. The extent of solvation of the alkali-metal cation varies from none (n = 0) for <NOBR>M[Al(NH-i-Pr)4]</NOBR> (2b, M = Li; 3b, M = Na) to n = 4 in the complex <NOBR>[Li(THF)4]</NOBR><NOBR>[Al(NH-p-tolyl)4]</NOBR> (2c), which exists as a solvent-separated ion pair. The complexes 2b, 3b, and <NOBR>[Na(THF)][Al(NH-p-tolyl)4]∞</NOBR> (3c) all exhibit one-dimensional polymeric structures in which the bis-N,N′-chelating <NOBR>tetrakis(amido)aluminate</NOBR> anions are bridged by four- (2b, 3b) and five-coordinate (3c) metal ions, respectively. The structures of two of the secondary products, <NOBR>{[Na(THF)2]</NOBR><NOBR>[(NH-t-Bu)Al(H)(µ-N-t-Bu)]}2<NOBR> (4) and <NOBR>{[Na(THF)3]</NOBR><NOBR>[(NH-</NOBR>p-tolyl)2Al(µ-N-p-tolyl)]}2</NOBR> (5), were established by X-ray crystallography. Complex 4 is a dimer of the <NOBR>[HAl(NH-t-Bu)(N-t-Bu)]–</NOBR> anion, which forms a central Al2N2 ring with each monoanion N,N′-chelated to a <NOBR>[Na(THF)2]+</NOBR> cation. Complex 5 is a dimer of the <NOBR>[Al(NR)(NHR)2]–</NOBR> (R = p-tolyl) anion in which the bridging p-tolyl groups are coordinated in an N-monodentate fashion to the trisolvated <NOBR>[Na(THF)3]+</NOBR> cations.
- Subjects
CHEMICAL reactions; AMINES; ORGANIC compounds; ALKALI metals; ALUMINATES
- Publication
Canadian Journal of Chemistry, 2006, Vol 84, Issue 3, p443
- ISSN
0008-4042
- Publication type
Article
- DOI
10.1139/V06-018