Structure of carboranyl derivatives of thallium(III)-crystal and molecular structure of (C,C?-dimethyl-m-carboran-9-yl)thallium chloride

Usyatinskii, A. Ya.; Bregadze, V. I.; Godovikov, N. N.; Vinogradova, L. E.; Leites, L. A.; Yanovskii, A. I.; Struchkov, Yu. T.

doi:10.1007/bf00948625

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“…The Tl−B distance is 2.311(2) Å, which is in good agreement with the sum of the covalent radii of thallium and boron , These data suggest that the thallium boron bond in 3 is relatively strong. This is borne out by other structural parameters such as the degree of geometrical change from planarity to tetrahedral in B(C 6 F 5 ) 3 , which has been used to gauge the strength of donor−acceptor complexes .…”

Section: Resultssupporting

confidence: 74%

Synthesis and Reactivity of Dimeric Ar‘TlTlAr‘ and Trimeric (Ar‘ ‘Tl)₃ (Ar‘, Ar‘ ‘ = Bulky Terphenyl Group) Thallium(I) Derivatives: Tl(I)−Tl(I) Bonding in Species Ligated by Monodentate Ligands

et al. 2005

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The synthesis and characterization of three new organothallium(I) compounds are reported. Reaction of (Ar'Li)(2) (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) and Ar"Li (Ar" = C(6)H(3)-2,6-(C(6)H(3)-2,6-Me(2))(2)) with TlCl in Et(2)O afforded (Ar'Tl)(2) (1) and (Ar' 'Tl)(3) (2). The "dithallene" 1 is the heaviest group 13 dimetallene and features a planar, trans-bent structure with Ar'Tl-Tl = 119.74(14) degrees and Tl-Tl = 3.0936(8) A. Compound 2 is the first structurally characterized neutral, three-membered ring species of formula c-(MR)(3) (M = Al-Tl; R = organo group). The Tl(3) ring has Tl-Tl distances in the range ca. 3.21-3.37 A as well as pyramidal Tl geometries. The Tl-Tl bonds in 1 and 2 are outside the range (2.88-2.97 A) of Tl-Tl single bonds in R(2)TlTlR(2) compounds. The weak Tl-Tl bonding in 1 and 2 leads to their dissociation into Ar'Tl and Ar' 'Tl monomers in hexane. The Ar'Tl monomer behaves as a Lewis base and readily forms a 1:1 donor-acceptor complex with B(C(6)F(5))(3) to give Ar'TlB(C(6)F(5))(3), 3. Adduct 3 features an almost linear thallium C(ipso)-Tl-B angle of 174.358(7) degrees and a Tl-B distance of 2.311(2) A, which indicates strong association. Treatment of 1 with a variety of reagents resulted in no reactions. The lower reactivity of 1 is in accord with the reluctance of Tl(I) to undergo oxidation to Tl(III) due to the unreactive character of the 6s(2) electrons.

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Section: Resultssupporting

confidence: 74%

Synthesis and Reactivity of Dimeric Ar‘TlTlAr‘ and Trimeric (Ar‘ ‘Tl)₃ (Ar‘, Ar‘ ‘ = Bulky Terphenyl Group) Thallium(I) Derivatives: Tl(I)−Tl(I) Bonding in Species Ligated by Monodentate Ligands

et al. 2005

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Structure of carboranyl derivatives of thallium(III)-crystal and molecular structure of (C,C?-dimethyl-m-carboran-9-yl)thallium chloride

Cited by 1 publication

References 12 publications

Synthesis and Reactivity of Dimeric Ar‘TlTlAr‘ and Trimeric (Ar‘ ‘Tl)₃ (Ar‘, Ar‘ ‘ = Bulky Terphenyl Group) Thallium(I) Derivatives: Tl(I)−Tl(I) Bonding in Species Ligated by Monodentate Ligands

Synthesis and Reactivity of Dimeric Ar‘TlTlAr‘ and Trimeric (Ar‘ ‘Tl)₃ (Ar‘, Ar‘ ‘ = Bulky Terphenyl Group) Thallium(I) Derivatives: Tl(I)−Tl(I) Bonding in Species Ligated by Monodentate Ligands

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Structure of carboranyl derivatives of thallium(III)-crystal and molecular structure of (C,C?-dimethyl-m-carboran-9-yl)thallium chloride

Cited by 1 publication

References 12 publications

Synthesis and Reactivity of Dimeric Ar‘TlTlAr‘ and Trimeric (Ar‘ ‘Tl)3 (Ar‘, Ar‘ ‘ = Bulky Terphenyl Group) Thallium(I) Derivatives: Tl(I)−Tl(I) Bonding in Species Ligated by Monodentate Ligands

Synthesis and Reactivity of Dimeric Ar‘TlTlAr‘ and Trimeric (Ar‘ ‘Tl)3 (Ar‘, Ar‘ ‘ = Bulky Terphenyl Group) Thallium(I) Derivatives: Tl(I)−Tl(I) Bonding in Species Ligated by Monodentate Ligands

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Synthesis and Reactivity of Dimeric Ar‘TlTlAr‘ and Trimeric (Ar‘ ‘Tl)₃ (Ar‘, Ar‘ ‘ = Bulky Terphenyl Group) Thallium(I) Derivatives: Tl(I)−Tl(I) Bonding in Species Ligated by Monodentate Ligands

Synthesis and Reactivity of Dimeric Ar‘TlTlAr‘ and Trimeric (Ar‘ ‘Tl)₃ (Ar‘, Ar‘ ‘ = Bulky Terphenyl Group) Thallium(I) Derivatives: Tl(I)−Tl(I) Bonding in Species Ligated by Monodentate Ligands