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Synthese, Kristallstrukturen und quantenchemische Untersuchung von Verbindungen mit leiterartigem Al 4 P 4 ‐ und hexagonal prismatischem Al 6 P 6 ‐Grundgerüst
Author(s) -
von Hänisch Carsten,
Weigend Florian
Publication year - 2002
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200202)628:2<389::aid-zaac389>3.0.co;2-b
Subject(s) - heptane , chemistry , crystallography , crystal structure , hexagonal crystal system , nuclear magnetic resonance spectroscopy , ether , single crystal , stereochemistry , organic chemistry
The reaction of AlCl 3 with Li 2 PR (R = Si i Pr 3 , SiMe i Pr 2 ) in a mixture of heptane and ether yields in the polycyclic compounds [(AlCl) 4 (μ 3 ‐PR) 2 (μ‐PR) 2 (Et 2 O) 2 ]( 1a : R = Si i Pr 3 ; 1b : SiMe i Pr 2 ) with a ladder‐shaped Al 4 P 4 core. The coordination sphere of the outer aluminium atoms in these compounds is completed by ether ligands. In contrast, the reaction of AlCl 3 with Li 2 PSi i Pr 3 in pure heptane yields in the formation of the hexagonal prismatic compound [(AlCl) 6 (μ 3 ‐PSi i Pr 3 ) 6 ]( 2 ). 1 and 2 were characterized by single crystal X‐ray diffraction analysis as well as by 31 P{1H} and 27 Al NMR spectroscopy. The structure determining effect of the solvent can be rationalized by quantumchemical calculations, which also show that the hexagonal prismatic structure is the most stable of the investigated oligomers in absence of ether.