Convenient One-Pot Synthesis and Structures of Pentaphenyltellurium Monohalides

Minoura, Mao; Sagami, and Takao; Akiba, Kin‐ya

doi:10.1021/om001075e

Cited by 15 publications

(21 citation statements)

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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. A singlet signal ( δ =600 ppm at −45 °C), which could be assigned to (4‐CF 3 C 6 H 4 ) 5 Te − K + C 8 , was observed by 125 Te NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 87%

“…Synthesis of Ar 5 TeCl (or Ar 5 TeBr) by the reaction of SO 2 Cl 2 (or Br 2 ) with Ar 5 Te − Li + : In our previous report,5c,d Ph 5 TeCl ( 2 b‐Cl ) and Ph 5 TeBr ( 2 b‐Br ) were prepared by halogenation of Ph 5 Te − Li + , which was prepared by the reaction of five equivalents of PhLi with one equivalent of TeCl 4 or TeBr 4. The reaction should be carried out at very low temperatures (−120 °C for 2 b‐X ).…”

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: 87%

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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“…The passage of acetylene gas through a solution of Se2Cl2 in CCl4 under pressure (10-12 atm., 30- molar ratio (designed to mimic "SeCl3") produces pure Se4N4 in 66 % yield [67], whereas the "SeCl3" generates Ph5TeLi, which is converted to pentaphenyltellurium halides Ph5TeX (X = Cl, Br) by treatment with SO2Cl2 or Br2 in a one-pot reaction [78].…”

Section: Diselenium 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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Convenient One-Pot Synthesis and Structures of Pentaphenyltellurium Monohalides

Abstract: Supporting Information Available: X-ray crystallographic details, including tables of positional parameters and bond lengths and angles and ORTEP drawings for 1a-c. This material is available free of charge via the Internet at http://pubs.acs.org. OM001075E

Cited by 15 publications

References 11 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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