Synthesis and characterization of hexaaryltellurium (TeAr6); the first neutral hexaarylated element compound

Minoura, Mao; Sagami, Takao; Miyasato, Masataka; Akiba, Kin‐ya

doi:10.1016/s0040-4020(97)00552-8

Cited by 12 publications

(13 citation statements)

References 62 publications

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“…Reductive cleavage of one of the TeC bonds in (4‐CF 3 C 6 H 4 ) 6 Te and the related hexaorganotellurium compounds: formation and reactions of Ar 5 Te − K + C 8 : As was previously communicated,5a,b (4‐CF 3 C 6 H 4 ) 6 Te showed remarkable stability toward chromatographic treatment, thermolysis (up to 300 °C) or photolysis, alkyllithium reagents (MeLi, n BuLi, or t BuLi), and some strong reducing reagents (lithium naphthalenide, 4,4′‐di‐ tert ‐butylbiphenylide, Na/K alloy, K, or Na/Hg amalgam etc.). However, we found recently that the reaction of (4‐CF 3 C 6 H 4 ) 6 Te with KC 8 proceeded smoothly even at −78 °C in THF and the expected anion (4‐CF 3 C 6 H 4 ) 5 Te − K + C 8 was generated quantitatively 5c.…”

Section: Resultsmentioning

confidence: 65%

“…Synthesis of hexaaryltellurium compounds based on the one‐pot procedure : In our previous report,5a,b (4‐CF 3 C 6 H 4 ) 6 Te ( 1 a ) was prepared by the one‐pot reaction of 4‐CF 3 C 6 H 4 Li and TeCl 4 in 16 % yield as shown in Scheme . But Ph 6 Te ( 1 b ) was prepared by the stepwise reaction of Ph 4 TeF 2 with PhLi since the one‐step procedure gave Ph 6 Te in only 0.5 % yield even after careful examination of the reaction conditions.…”

Section: Resultsmentioning

confidence: 99%

“…Preparative gel permeation liquid chromatography (HPLC) was performed by LC‐908 equipped with JAIGEL‐1H and ‐2H columns (Japan Analytical Industry) with 1,2‐dichloroethane as a solvent. Compounds 1 a 5a,b and 2 b 5c were prepared by published procedures.…”

Section: Methodsmentioning

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: 65%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

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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“…Subsequently, however, it was shown that pure SeCl2 is readily obtained by treatment of elemental selenium with an equimolar amount of SO2Cl2 (eq. 7) in THF; such solutions are stable towards disproportionation for 1 day at 23 o C as determined by 77 Se NMR spectroscopy [21]. Similarly, the facile preparation of solutions of pure selenium dibromide is achieved by treatment of grey selenium with bromine (Br2) in a chlorocarbon solvent such as CHCl3 or CCl4 (eq.…”

Section: Selenium Dihalidesmentioning

confidence: 99%

2. Selenium– and tellurium–halogen reagents

Chivers¹,

Laitinen²

2019

Selenium and Tellurium Reagents

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Selenium and tellurium form binary halides in which the chalcogen can be in formal oxidation states (IV), (II) or (I). They are versatile reagents for the preparation of a wide range of inorganic and organic selenium and tellurium compounds taking advantage of the reactivity of the chalcogenhalogen bond. With the exception of the tetrafluorides, the tetrahalides are either commercially available or readily prepared. On the other hand, the low-valent species, EX2 (E = Se, Te; X = Cl, Br) and E2X2 (E = Se, Te; X = Cl, Br) are unstable with respect to disproportionation and must be used as in situ reagents. Organoselenium and tellurium halides are well-known in oxidation states (IV) and (II), as exemplified by REX3, R2EX2, and REX (R = alkyl, aryl; E = Se, Te; X = F, Cl, Br, I), as well as mixed-valent (IV/II) compounds of the type RTeX2TeR are also known. This chapter surveys the availability and/or preparative methods for these widely used reagents followed by examples of their applications in synthetic inorganic and organic selenium and tellurium chemistry. For both the binary halides and their organic derivatives the discussion is subdivided according to the formal oxidation state of the chalcogen.

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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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Synthesis and characterization of hexaaryltellurium (TeAr6); the first neutral hexaarylated element compound

Cited by 12 publications

References 62 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

2. Selenium– and tellurium–halogen reagents

Hypervalent Derivatives of Selenium and Tellurium

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