From the Lithium‐2‐anilide‐2‐fluoro‐1,3‐diaza‐2‐sila‐cyclopentene‐GaCl3 Adduct to 1,4,6‐Triaza‐5‐gallium‐7‐sila‐cyclo‐3‐heptene ‐ Experimental and Quantum‐chemical Results |
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| Authors: | Andreas Fischer Daniel Stern Andrea Thorn Sascha Abraham Dietmar Stalke Uwe Klingebiel Prof Dr |
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| Institution: | 1. Institut für Anorganische Chemie, Georg‐August‐Universit?t, Tammannstr. 4, 37077 G?ttingen, Germany;2. Institut für Physikalische Chemie, Georg‐August‐Universit?t, Tammannstr. 6, 37077 G?ttingen, Germany |
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| Abstract: | The lithium salt (HC–NCMe3)2SiFNLiR ( 1 ) R = C6H3(2,6‐CHMe2)2 reacts with trichlorogallium under displacement of the lithium ion by GaCl3 to give the adduct (HC–NCMe3)2SiFN]– (GaCl3)R·Li(thf)4]+ ( 1 ). Compound 1 thermally loses LiCl and forms the bicyclic ring intermediates V and VI . Compound VI adds the aniline H2NC6H3(2,6‐CHMe2)2 and the unsaturated, seven‐membered ring compound –NCMe3–CH2–CH=NCMe3GaCl2–NR–SiFNHR– ( 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. |
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| Keywords: | Gallium Silicon Ring intermediates Proton migration Computational chemistry |
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