The Reactivity of Bis(para‐methoxyphenyl)telluroxide towards Triflic Acid and Diphenylphosphinic Acid. Theoretical Considerations of the Protonation and Hydration Process of Diorganotelluroxanes

Abstract

The reaction of (p‐MeOC6H4)2TeO with two equivalents of HO3SCF3 and HO2PPh2 provided the tetraorganoditelluroxanes (F3CSO3)(p‐MeOC6H4)2TeOTe(p‐MeOC6H4)2(O3SCF3) (1) and (Ph2PO2)(p‐MeOC6H4)2TeOTe(p‐MeOC6H4)2(O2PPh2)·2 Ph2PO2H (2) in good yields. Compounds 1 and 2 were characterized by solution and solid‐state 31P and 125Te NMR spectroscopy, IR spectroscopy, electrospray mass spectrometry, conductivity measurements and single crystal X‐ray diffraction. In solution, compound 1 undergoes an electrolytic dissociation and reversibly reacts with traces of water to give the mononuclear cation [(p‐MeOC6H4)2TeOH]+ and triflate anions. Theoretical aspects of the protonation and hydration of model telluroxanes R2TeO (R = H, Me, Ph) were investigated by preliminary DFT calculations and compared to the corresponding selenoxanes R2SeO. The tellurium dihydroxides R2Te(OH)2 seem to be more stable than the hydrogen‐bonded complexes R2TeO·H2O.

A survey of tellurium-centered secondary-bonding supramolecular synthons

“…Hydrogen atoms have been omitted for clarity. Original data from Refs [40][41][42][43][44][45][46][47][48]…”

The structural diversity of Te–I interactions within tetraorganoditelluroxane diiodides and related compounds

“…In addition to the two axial I atoms (I1, I1a), there are two I atoms (I2, I2a) associated with the Te atoms via longer secondary interactions of average 3.612(2) Å . In this way, the overall crystal structure of 3 closely resembles that of the tetraorganoditelluroxane ditriflate [(p-MeOC 6 H 4 ) 2 Te] 2 O(O 3 SCF 3 ) 2 [8]. The Te-O-Te angle of 3 being 118.8(2)°compares well with the corresponding angle in [(p-MeOC 6 H 4 ) 2 Te] 2 O(O 3 SCF 3 ) 2 (120.2(3)°) and related tetraorganoditelluroxanes [8].…”

“…In this way, the overall crystal structure of 3 closely resembles that of the tetraorganoditelluroxane ditriflate [(p-MeOC 6 H 4 ) 2 Te] 2 O(O 3 SCF 3 ) 2 [8]. The Te-O-Te angle of 3 being 118.8(2)°compares well with the corresponding angle in [(p-MeOC 6 H 4 ) 2 Te] 2 O(O 3 SCF 3 ) 2 (120.2(3)°) and related tetraorganoditelluroxanes [8]. The primary coordination sphere of 3 is also reminiscent of the molecular structure of hexaphenyldistiboxane diiodide (Ph 3 Sb) 2 OI 2 [9].…”

“…The base hydrolysis of C 4 H 8 TeI 2 (8) with an excess of aqueous NaOH solution afforded the tritelluroxane diiodide (C 4 H 8 Te) 3 O 2 I 2 (9) in excellent yield as colourless crystals …”

Recent advances in spirochalcogenurane stereochemistry—A mini review

“…This parallels the well-known tendency of the oxides to exist as hydrates in water solution because of stabilization of the chalcogen-oxygen single bonds. [44][45][46] While sulfoxides do not form hydrates, the corresponding telluroxides are completely hydrated in water. The selenoxides are stabilized by hydrogen bonding to a water molecule, as demonstrated by both X-ray crystallography and DFT calculations.…”