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Browse Prior Art Database

Bi Tetrathiafulvalene and Bi Tetraselenafulvalene

IP.com Disclosure Number: IPCOM000052761D
Original Publication Date: 1981-Jul-01
Included in the Prior Art Database: 2005-Feb-11
Document File: 3 page(s) / 41K

Publishing Venue

IBM

Related People

Green, DC: AUTHOR [+3]

Abstract

Although in the past a large variety of tetrathiafulvalene (TTF) and tetraselenafulvalene (TSeF) derivatives have been prepared, no molecules have appeared in the literature in which TTF or TSeF units are linked together by single bonds. We have now found a high yield single-step synthesis of dimeric tetrathiafulvalene and tetraselenafulvalene. These compounds are shown in the figure below and generalized therein as structure 4.

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Bi Tetrathiafulvalene and Bi Tetraselenafulvalene

Although in the past a large variety of tetrathiafulvalene (TTF) and tetraselenafulvalene (TSeF) derivatives have been prepared, no molecules have appeared in the literature in which TTF or TSeF units are linked together by single bonds. We have now found a high yield single-step synthesis of dimeric tetrathiafulvalene and tetraselenafulvalene. These compounds are shown in the figure below and generalized therein as structure 4.

We have also found a multi-step preparation of bi-TTF, authenticating unequivocally the assigned structure for compound 1. This latter procedure also provided a method whereby the first ~examples of ter-TTF compounds were synthesized.

Monolithio TTF or TSeF, formed by the action of butyl lithium or lithium diisopropyl amide on TTF or TSeF, can be reacted with various copper reagents, for example, tetrakis [Iodo(Tri-n-Butyl Phospine)-Copper (1)], followed by oxygen treatment to afford in one synthetic step dimeric products. These oligomeric TTF or TSeF species have proved useful as CT donor molecules forming complexes possessing unique properties.

For the step-wise independent synthesis of TTF oligomers, our synthetic strategy was to concentrate on the preparation of 4-tetrathiafulvalenyl-1,3-dithiol- 2-one. This molecule was elaborated by the reaction of lithio TTF with ethylchloroacetate to yield chloroacetyl TTF, which reacted readily in refluxing alcohol with potassium 0-ethyl xanthate. Smooth cyclization of the resulting xanthate into the pivotal 2-oxo-dithiocarbonate was realized on treatment with an HBr saturated acetic acid solution.

Cross-coupling of the resulting dithiocarbonate with either vinylene dithia or trithia carbonate was accomplished by slow addition to a refluxing solution of the dithiocarbonate in neat triethyl phosphite, affording bi-TTF 1 identical with samples obtained previously by the single-step method.

Also prepared by this multi-s...