Jens Bolsinger

Intramolecularly Coordinated Telluroxane Clusters and Polymers

The stoichiometrically controlled chlorination of the diarylditelluride (8-Me(2) NC(10) H(6) Te)(2) with SO(2) Cl(2) afforded the aryltellurinyl chloride 8-Me(2) NC(10) H(6) TeCl (1) and the aryltellurium trichloride 8-Me(2) NC(10) H(6) TeCl(3) (2). Alternatively, 1 was obtained by the reaction of the aryltellurenyl diethyldithiacarbamate 8-Me(2) NC(10) H(6) Te(S(2) CNEt(2) ) with hydrochloric acid. The base hydrolysis of 2 provided the novel telluroxanes (8-Me(2) NC(10) H(6) Te)(2) OCl(4) (3), (8-Me(2) NC(10) H(6) Te)(6) O(5) Cl(8) (4), (8-Me(2) NC(10) H(6) Te)(6) O(8) Cl(2) (5), [(8-Me(2) NC(10) H(6) Te)(2) O(3) ](n) (6) and (8-Me(2) NC(10) H(6) Te)(6) O(8) (OH)(2) (7) depending on the reaction conditions applied. The reaction of 7 with ClTe(OiPr)(3) in the presence of water gave rise to the telluroxane (8-Me(2) NC(10) H(6) Te)(6) Te(2) O(12) Cl(2) (8). The crystal and molecular structures of 1-3 and 5-8 were determined by X-ray crystallography. The telluroxane clusters and polymers 6-8 hold potential as model compounds for alkali tellurite glasses (M(2) O)(x) (TeO(2) )(1-x) (M=Li, Na, K) for which no precise structural data are available.

Mesityltellurenyl Cations Stabilized by Triphenylpnictogens [MesTe(EPh3)]+ (E = P, As, Sb)

The homoleptic 1:1 Lewis pair (LP) complex [MesTe(TeMes2)]O3SCF3 (1) featuring the cation [MesTe(TeMes2)](+) (1a) was obtained by the reaction of Mes2Te with HO3SCF3. The reaction of 1 with Ph3E (E = P, As, Sb, Bi) proceeded with substitution of Mes2Te and provided the heteroleptic 1:1 LP complexes [MesTe(EPh3)]O3SCF3 (2, E = P; 3, E = As) and [MesTe(SbPh3)][Ph2Sb(O3SCF3)2] (4) featuring the cations [MesTe(EPh3)](+) (2a, E = P; 3a, E = As; 4a, E = Sb) and the anion [Ph2Sb(O3SCF3)2](-) (4b). In the reaction with Ph3Bi, the crude product contained the cation [MesTe(BiPh3)](+) (5a) and the anion [Ph2Bi(O3SCF3)2](-) (5b); however, the heteroleptic 1:1 LP complex [MesTe(BiPh3)][Ph2Bi(O3SCF3)2] (5) could not be isolated because of its limited stability. Instead, fractional crystallization furnished a large amount of Ph2BiO3SCF3 (6), which was also obtained by the reaction of Ph3Bi with HO3SCF3. The formation of the anions 4b and 5b involves a phenyl group migration from Ph3E (E = Sb, Bi) to the MesTe(+) cation and afforded MesTePh as the byproduct, which was identified in the mother liquor. The heteroleptic 1:1 LP complexes 2-4 were also obtained by the one-pot reaction of Mes2Te, Ph3E (E = P, As, Sb) and HO3SCF3. Compounds 1-4 and 6 were investigated by single-crystal X-ray diffraction. The molecular structures of 1a-4a were used for density functional theory calculations at the B3PW91/TZ level of theory and studied using natural bond order (NBO) analyses as well as real-space bonding descriptors derived from an atoms-in-molecules (AIM) analysis of the theoretically obtained electron density. Additionally, the electron localizability indicator (ELI-D) and the delocalization index are derived from the corresponding pair density.

Diarylhalotelluronium(IV) cations [(8-Me2NC10H6)2TeX]+ (X = Cl, Br, I) stabilized by intramolecularly coordinating N-donor substituents

The stoichiometrically controlled halogenation of the intramolecularly coordinated diaryltelluride (8-Me2NC10H6)2Te using SO2Cl2, Br2 and I2 was studied. At an equimolar ratio, the diarylhalotelluronium cations [(8-Me2NC10H6)2TeX](+) (1, X = Cl; 2, X = Br; 3, X = I) formed and were isolated as 1·Cl(-)·H2O·1/2THF, 2·Br(-), and 3·I(-), respectively. When the same reactions were carried out in the presence of KPF6, 1·PF6(-) and 22·Br(-)·PF6(-) were obtained. The chlorination of (8-Me2NC10H6)2Te with an excess of SO2Cl2 occurred with a double electrophilic substitution at the 8-dimethylaminonaphthyl residues (in the ortho- and para-positions) and afforded the diaryltellurium dichloride (5,7-Cl2-8-Me2NC10H4)2TeCl2 (4). The bromination of (8-Me2NC10H6)2Te with three equivalents of Br2 took place with a single electrophilic substitution at the 8-dimethylaminonaphthyl residues (in the para-positions) and provided the diaryltellurium dibromide (5-Br-8-Me2NC10H5)2TeBr2 (5), while an excess of Br2 produced the diarylbromotelluronium cation [(5-Br-8-Me2NC10H5)2TeBr](+) (6) that was isolated as 6·Br3(-). The reaction of (8-Me2NC10H6)2Te with two or three equivalents of iodine provided 3·I3(-) and 3·I3(-)·I2, respectively. In the presence of water, 1·Cl(-)·H2O·1/2THF, 2·Br(-), 3·I(-) and 3·I3(-) hydrolyzed to give the previously known diarylhydroxytelluronium cation [(8-Me2NC10H6)2TeOH](+) (7) that was isolated as 7·Cl(-), 7·Br(-)·H2O·THF, 7·I(-) and 7·I3(-)·H2O, respectively. The molecular structures of 1-7 were investigated in the solid-state by (125)Te MAS NMR spectroscopy and X-ray crystallography and in solution by multinuclear NMR spectroscopy ((1)H, (13)C, (125)Te), electrospray mass spectrometry and conductivity measurements. The stabilization of cations 1-3 by the intramolecular coordination was estimated by DFT calculations at the B3PW91/TZ level of theory.

The Reactivity of Diorganotellurium Oxides Towards Phenol and o-Nitrophenol. Hypervalent and Secondary Bonding of Four Different Product Classes

The reaction of the diorganotellurium oxides R2TeO (R = Ph, p-MeOC6H4, p-Me2NC6H4) with phenol and o-nitrophenol produces diorganotellurium hydroxy phenolates, R2Te(OH)OPh (1, R = Ph; 2, R = p-MeOC6H4; 3, R = p-Me2NC6H4), diorganotellurium bis(phenolates) R2Te(OPh)2 (4, R = Ph; 5, R = p-MeOC6H4; 6, R = p-Me2NC6H4), tetraorganoditelluroxane bis(o-nitrophenolates), (R′O)R2TeOTeR2(OR′) (7, R = p-MeOC6H4; 8, R = p-Me2NC6H4; R′ = o-NO2C6H4), and a hexaphenyltritelluroxane bis(o-nitrophenolate) (R′O)Ph2TeOTePh2OTePh2(OR′) (9, R′ = o-NO2C6H4), respectively. The redistribution reactions of R2Te(OPh)2 (4, R = Ph; 5, R = p-MeOC6H4; 6, R = p-Me2NC6H4) with the corresponding diorganotellurium oxides R2TeO and diorganotellurium dichlorides R2TeCl2 (R = Ph, p-MeOC6H4, p-Me2NC6H4) give rise to the formation of moisture sensitive tetraorganoditelluroxane bis(phenolates) (PhO)R2TeOTeR2(OPh) (10, R = Ph; 11, R = p-MeOC6H4; 12, R = p-Me2NC6H4) and diorganotellurium chloro phenolates, R2Te(Cl)OPh (13, R = Ph; 14, R = p-MeOC6H4; 15, R = p-Me2NC6H4), respectively. The reaction of the diorganotellurium oxides R2TeO with the corresponding diorganotellurium dichlorides R2TeCl2 (R = Ph, p-MeOC6H4, p-Me2NC6H4) affords tetraorganoditelluroxane dichlorides ClR2TeOTeR2Cl (16, R = Ph; 17, R = p-MeOC6H4; 18, R = p-Me2NC6H4) as air-stable solid materials. The reactivity of 1–18 can be rationalized by the kinetic lability of the Te–O and Te–Cl bonds. Compounds 1–18 have been characterized by solution and solid-state 125Te NMR spectroscopy and 2, 4, 6, 7, 9, 17, and 18 have also been analyzed by X-ray crystallography.

Oxygen Transfer from an Intramolecularly Coordinated Diaryltellurium Oxide to Acetonitrile. Formation and Combined AIM and ELI-D Analysis of a Novel Diaryltellurium Acetimidate

The reaction of the intramolecularly coordinated diaryltellurium(IV) oxide (8-Me2NC10H6)2TeO with acetonitrile proceeds with oxygen transfer and gives rise to the formation of the novel zwitterionic diaryltelluronium(IV) acetimidate (8-Me2NC10H6)2TeNC(O)CH3 (1) in 57% yield. Hydrolysis of 1 with hydrochloric acid affords acetamide and the previously known diarylhydroxytelluronium(IV) chloride [(8-Me2NC10H6)2Te(OH)]Cl.

Synthesis and structure of diarylhalotelluronium hexahalotellurates [(8-Me2 NC10 H6)2 TeX]2 TeX6 (X=Cl, Br)

Abstract The title compounds [(8-Me2 NC10 H6)2 TeX]2 TeX6 (1, X=Cl; 2, X=Br) were obtained by the oxidation of (8-Me2 NC10 H6)2 Te with SO2 Cl2 and Br2 and the subsequent addition of TeCl4 and TeBr4, respectively, and were characterized by X-ray crystallography and multinuclear NMR spectroscopy. Due to the intramolecularly coordinating 8-dimethylaminonaphthyl substituents, 1 and 2 comprise loosely associated ion pairs of distorted trigonal bipyramidal [(8-Me2 NC10 H6)2 TeX]+ cations and octahedral TeX62-

Two polymorphs of dimesityltellurium dichloride

{\rm{TeX}}_{\rm{6}}^{{\rm{2 - }}}

New insights into the formation and structure of diaryl tritellurides

anions (X=Cl, Br).

A Well-Defined Dinuclear Telluronic Acid [RTe(μ-O)(OH)3]2

Abstract The title compound Mes2TeCl2 crystallises from CHCl3 as colourless plates and needles that turned out to be triclinic and monoclinic modifications. Both polymorphs have been investigated by X-ray crystallography. The molecular structures are very similar. Crystal packing effects have only a marginal influence on the structural parameters.