Premium
From the Lithium‐2‐anilide‐2‐fluoro‐1,3‐diaza‐2‐sila‐cyclopentene‐GaCl 3 Adduct to 1,4,6‐Triaza‐5‐gallium‐7‐sila‐cyclo‐3‐heptene ‐ Experimental and Quantum‐chemical Results
Author(s) -
Fischer Andreas,
Stern Daniel,
Thorn Andrea,
Abraham Sascha,
Stalke Dietmar,
Klingebiel Uwe
Publication year - 2010
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/zaac.201000041
Subject(s) - chemistry , lithium (medication) , adduct , gallium , ring (chemistry) , crystallography , tautomer , imine , medicinal chemistry , stereochemistry , organic chemistry , medicine , endocrinology , catalysis
The lithium salt (HC–NCMe 3 ) 2 SiFNLi R ( 1 ) R = C 6 H 3 (2,6‐CHMe 2 ) 2 reacts with trichlorogallium under displacement of the lithium ion by GaCl 3 to give the adduct [(HC–NCMe 3 ) 2 SiFN] – [(GaCl 3 ) R ·Li(thf) 4 ] + ( 1 ). Compound 1 thermally loses LiCl and forms the bicyclic ring intermediates V and VI . Compound VI adds the aniline H 2 NC 6 H 3 (2,6‐CHMe 2 ) 2 and the unsaturated, seven‐membered ring compound –NCMe 3 –CH 2 –CH=NCMe 3 GaCl 2 –N R –SiFNH R – ( 2 ) is obtained. The addition is accompanied by an enamine‐imine‐tautomerism and proves the Lewis acid character of the silicon atom in an unknown 3‐center‐2‐electron interaction of one nitrogen atom with the silicon and gallium atoms. Quantum chemical calculations of the thermal isomerisation process and crystal structures of 1 and 2 are reported.