Novel Valence Expansion Reactions Using KC8: A New Route to Hexavalent Organotellurium Compounds from Divalent Tellurium

Miyasato, Masataka; Minoura, Mao; Yamamoto, Yohsuke; Akiba, Kin‐ya

doi:10.1246/cl.2002.288

Cited by 6 publications

(3 citation statements)

References 19 publications

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“…X‐ray analysis of trans ‐ 6 a confirmed the octahedral structure, which was similar to that of trans ‐ 4 a . The two 4‐CF 3 C 6 H 4 groups in trans ‐ 6 a were located trans to each other 5f.…”

Section: Resultsmentioning

confidence: 99%

“…Then KC 8 transferred electrons to Ar 2 Te to form the dianion species, Ar 2 Te 2− , followed by reactions with electrophilic reagents and KC 8 successively. Since the hypothetical mechanism indicated a possible new method for generation of hexaorganotellurium compounds from divalent organotellurium, the reaction of KC 8 with Ar 2 Te and other low‐valent organotellurium compounds are examined 5f.…”

Section: Resultsmentioning

confidence: 99%

“…Although considerable attention has been paid to the hypervalency of some tetraorganotellurium compounds,3 of the hexavalent organotellurium compounds bearing more than five TeC bonds, (CH 3 ) 6 Te4 was the only structurally characterized compound until our recent reports 5. 6 We reported several new synthetic procedures for novel types of hexavalent organotellurium compounds bearing five or six TeC bonds; 1) first synthesis of (4‐CF 3 C 6 H 4 ) 6 Te ( 1 a ) by one‐pot reaction of 4‐CF 3 C 6 H 4 Li and TeCl 4 together with synthesis of Ph 6 Te ( 1 b ) by reaction of Ph 4 TeF 2 with PhLi,5a,b 2) Ph 5 TeCl ( 2 b ‐Cl) and Ph 5 TeBr ( 2 b ‐Br) by the reaction of SO 2 Cl 2 or Br 2, respectively, with Ph 5 Te − Li + generated from TeCl 4 or TeBr 4 with five equivalents of PhLi,5c,d 3) (4‐CF 3 C 6 H 4 ) 5 (CH 3 )Te ( 3 a ) from (4‐CF 3 C 6 H 4 ) 5 Te − K + C 8 by treatment with CH 3 I, 5e and 4) (4‐CH 3 C 6 H 4 ) 5 (CH 3 )Te ( 3 c ) from (4‐CH 3 C 6 H 4 ) 2 Te by treatment with KC 8 followed by reaction with CH 3 I 5f. These methods recently reported by us are illustrated in Scheme .…”

Section: Introductionmentioning

confidence: 99%

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Syntheses and Reactions of Hexavalent Organotellurium Compounds Bearing Five or Six TelluriumCarbon Bonds

Miyasato

Sagami

Minoura

et al. 2004

Chemistry A European J

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A variety of hexaorganotellurium compounds, Ar(6-n)(CH3)nTe [Ar=4-CF3C6H4, n=0 (1a), n=1 (3a), n=2 (trans-4a and cis-4a), n=3 (mer-5a), n=4 (trans-6a); Ph, n=0 (1b), n=1 (3b), n=2 (trans-4b); 4-CH3C6H4, n=0 (1c), n=1 (3c), n=2 (trans-4c), n=4 (trans-6c); 4-BrC6H4, n=0 (1d)] and Ar5(R)Te [Ar=4-CF3C6H4, R=4-CH3OC6H4 (8); Ar=4-CF3C6H4, R=vinyl (9), Ar=Ph, R=vinyl (10), Ar=4-CF3C6H4, R=PhSCH2 (11), Ar=Ph, R=PhSCH2 (12), Ar=4-CF3C6H4, R=nBu (13)] and pentaorganotellurium halides, Ar5TeX [Ar=4-CF3C6H4, X=Cl (2a-Cl), X=Br (2a-Br); Ar=Ph, X=Cl (2b-Cl), X=Br (2b-Br); Ar=4-CH3C6H4, X=Cl (2c-Cl), X=Br (2c-Br); Ar=4-BrC6H4, X=Br (2d-Br)] and (4-CF3C6H4)4(CH3)TeX [X=Cl (trans-7a-Cl) and X=Br (trans-7a-Br)] were synthesized by the following methods: 1) one-pot synthesis of 1 a, 2) the reaction of SO2Cl2 or Br2 with Ar5Te(-)Li+ generated from TeCl4 or TeBr4 with five equivalents of ArLi, 3) reductive cleavage of Ar(6-m)(CH3)(m)Te (m=0 or 2) with KC8 followed by treatment with CH3I, 4) valence expansion reaction from low-valent tellurium compounds by treatment with KC8 followed by reaction with CH3I, 5) nucleophilic substitution of Ar(6-y-z)(CH3)zTeX(y-z) (X=Cl, Br, OTf; z=0, 1; y=1, 2) with organolithium reagents. The scope and limitations and some details for each method are discussed and electrophilic halogenation of the hexaorganotellurium compounds is also described.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Syntheses and Reactions of Hexavalent Organotellurium Compounds Bearing Five or Six TelluriumCarbon Bonds

Miyasato

Sagami

Minoura

et al. 2004

Chemistry A European J

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Hypervalent Derivatives of Selenium and Tellurium

Drabowicz

Kiełbasiński

Zając

2011

Patai's Chemistry of Functional Groups

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The chapter presents the advances in the chemistry of hypervalent derivatives of selenium and tellurium that have emerged in recent years (usually after 1998). These are based on the inclusion of the discussed compounds into particular subsections, arising from the N‐Ch‐L (A n B m ) coding system, in which N stands for the number of valence electrons associated formally with a central chalcogen atom and L shows the number of ligands (A and B stand for the bonding element). The chapter begins with a brief discussion on the nature of bonding, molecular geometry, basic reactivity and pseudorotation mechanisms in hypervalent selenium and tellurium molecules which can be described as 10‐Ch‐4 and 10‐Ch‐5 and 12‐Ch‐6 species. Next, the unstable hypervalent selenium and tellurium structures detected as reactive intermediates are discussed. The remaining part of the chapter is devoted to the presentation of the chemistry of stable compounds. The isolable derivatives are presented in the following order: selenuranes and telluranes, 10‐Ch‐5 and 12‐Ch‐5 species, 10‐Ch‐6 complexes of perchalcogenuranes with Lewis bases, 12‐Ch‐6 perchalcogenuranes, 12‐Ch‐5 perchalcogenuranes, and 2N‐Ch‐N charged pertelluranes (Ch = Te, N > 6).

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Recent Advances of Structural Chemistry of Organoselenium and Organotellurium Compounds

Nakanishi

Hayashi

Hashimoto

et al. 2014

Patai's Chemistry of Functional Groups

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The recent advances of structural chemistry of organoselenium and organotellurium compounds are reviewed. The basic concepts of structural chemistry of the compounds are well summarized in Chapter 3 of Volume 1 in this series. About 9,000 structures for the compounds have been reported since then, therefore only selected results can be discussed here. Such compounds are expected to contain at least one CE (E = Se or Te) bond, although those with no CE bonds are also discussed, as necessary. Compounds containing CE (E = Se and Te) are discussed in some detail. Structures of unstable and/or reactive species are explained in detail, which are stabilized by the formation of dimers or higher oligomers or using large protecting groups. Bis‐selenides and bis‐tellurides and the derivatives at the naphthalene 1,8‐positions and the related systems are discussed in detail. The compounds containing hypervalent interactions are also discussed in detail. The idea is applied to the intramolecular and intermolecular linear interactions in crystals. In this connection, the extended hypervalent interactions are also explained in detail for the linear interactions longer than three, exemplified by typical cases and unique cases in crystals.

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Novel Valence Expansion Reactions Using KC8: A New Route to Hexavalent Organotellurium Compounds from Divalent Tellurium

Abstract: Hexavalent tellurium compounds, Ar5(CH3)Te, Ar4(CH3)2Te, and Ar2(CH3)4Te (Ar=4-CF3C6H4, Ph, 4-CH3C6H4), were synthesized by the reaction of Ar2-n(CH3)nTe (n=0–1) or Ar3-m(CH3)mTe+X- (m=0–2) with KC8 followed by the treatment with CH3I.

Cited by 6 publications

References 19 publications

Syntheses and Reactions of Hexavalent Organotellurium Compounds Bearing Five or Six TelluriumCarbon Bonds

Syntheses and Reactions of Hexavalent Organotellurium Compounds Bearing Five or Six TelluriumCarbon Bonds

Hypervalent Derivatives of Selenium and Tellurium

Recent Advances of Structural Chemistry of Organoselenium and Organotellurium Compounds

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