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The interaction of 1,2:5,6:9,10-tribenzocyclododeca-1,5,9-triene-3,7,11-triyne with transition metals and alkali metals

by Djegli, Abdellah

Abstract (Summary)
The interactions of 1,2:5,6:9,10-tribenzocyclododeca-1,5,9-triene-3,7,11-triyne (TBC) with alkali metals (Li, Na, and K) and transition metals are described. An unprecedented lithium induced alkyne cyclization reaction of TBC to form a novel helicene dianion is described. The novel dicyclopentadiene dianion, (Li(TMEDA)) 2(C24H14), has been characterized by IR, NMR and X-ray analysis. The X-ray analysis shows that the two helicene enantiomorphs co-crystallize with each of the cyclopentadienyl rings ?-bound to a lithium cation which in turn is chelated by a TMEDA molecule. A mechanism for the lithium induced cyclization reaction of TBC is proposed. Protonation and silylation reactions of (Li(TMEDA)) 2(C24H14) are examined. The syntheses of C24H16 and ( C24H14)(SiMe3)2 are described. These compounds have been characterized by IR, NMR and X-ray analysis. The molecular structure of ( C24H14)(SiMe3)2 shows the helical character of this compound. The synthesis and characterization of the first 12 membered macrocycle transition metal sandwich complexes is described. The complex (Ag(TBC)2(OTf)).TBC.C6H14 has been characterized by IR, NMR, and X-ray analysis. The unit cell contains a staggered and an ec lipsed bis(TBC)Ag(I) sandwich, two free TBC molecules, two triflate anions and a disordered hexane solvent molecule. A tetracobalt cluster of TBC is described. The complex Co4(TBC)(CO)9 has been characterized by IR and X-ray analysis. The X-ray analysis of Co4(TBC)(CO)9 shows an unusual arrangement of cobalt atoms. It is the first example of a cobalt cluster with one cobalt bound to three other cobalt atoms that are not bound to each other.
Bibliographical Information:

Advisor:

School:Case Western Reserve University

School Location:USA - Ohio

Source Type:Master's Thesis

Keywords:tribenzocyclododeca transition alkali metals

ISBN:

Date of Publication:01/01/1991

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