TY - JOUR
T1 - Isolation and structural characterization of some aryltellurium halides and their hydrolyzed products stabilized by an intramolecular Te⋯N interaction
AU - Srivastava, Kriti
AU - Shah, Poonam
AU - Singh, Harkesh B.
AU - Butcher, Ray J.
PY - 2011/2/14
Y1 - 2011/2/14
N2 - The isolation of pure [2-(phenylazo)phenyl-C,N′]tellurium(IV) tribromide (6) has been achieved by modifying the reported procedure, which involved transmetalation of [2-(phenylazo)phenyl-C,N′]mercury(II) chloride (7) with TeBr4. The mixed-valent derivative bis[2-(phenylazo)phenyl- C,N′]ditellurium dichloride (19), incorporating both a divalent and a tetravalent tellurium, was obtained serendipitously during the reduction of [2-(phenylazo)phenyl-C,N′]tellurium(IV) trichloride (16) with hydrazine hydrate. Bis[2-(phenylazo)phenyl-C,N′]telluride (10) has been synthesized by the ortho-lithiation route. Telluride 10, on treatment with SO 2Cl2 and Br2, underwent oxidative addition to give the expected Te(IV) halogenated products bis[2-(phenylazo)phenyl-C, N′]tellurium(IV) dichloride (13) and bis[2-(phenylazo)phenyl-C,N′] tellurium(IV) dibromide (11), respectively. However, a similar reaction of 10 with I2 resulted in the formation of an unexpected telluronium cation, iodobis[2-(phenylazo)phenyl-C,N′]telluronium triiodide (14), and [2-(phenylazo)phenyl-C,N′]tellurenenyl(II) iodide (12). Alkaline hydrolysis of 16 under reflux conditions resulted in the formation of monomeric [2-(phenylazo)phenyl-C,N′]tellurinic acid (20) and its sodium salt (21) as a cocrystal. Bis[[2-(phenylazo)phenyl-C,N′]tellurium]oxide (22) was obtained from the hydrolysis of [2-(phenylazo)phenyl-C,N′]tellurium(II) chloride (17). The reaction of 13 with an alkaline solution resulted in the formation of the corresponding bis[2-(phenylazo)phenyl-C,N′]tellurium(IV) oxide (23) and dichlorobis[2-(phenylazo)phenyl-C,N′]tellurium(IV) oxide (24). The identity of all the derivatives was confirmed by multinuclear NMR (1H, 13C, 125Te) and FT-IR spectroscopy, elemental analysis, and ESI-MS. The structures for tellurium derivatives 6, 10-14, 17, 19, 20-23, and 23A were also confirmed by X-ray crystallography. Density functional theory (DFT) was utilized for optimizing the geometries of 11, 13, and 14 to examine the possibility of a four-membered intramolecular Te⋯N interaction.
AB - The isolation of pure [2-(phenylazo)phenyl-C,N′]tellurium(IV) tribromide (6) has been achieved by modifying the reported procedure, which involved transmetalation of [2-(phenylazo)phenyl-C,N′]mercury(II) chloride (7) with TeBr4. The mixed-valent derivative bis[2-(phenylazo)phenyl- C,N′]ditellurium dichloride (19), incorporating both a divalent and a tetravalent tellurium, was obtained serendipitously during the reduction of [2-(phenylazo)phenyl-C,N′]tellurium(IV) trichloride (16) with hydrazine hydrate. Bis[2-(phenylazo)phenyl-C,N′]telluride (10) has been synthesized by the ortho-lithiation route. Telluride 10, on treatment with SO 2Cl2 and Br2, underwent oxidative addition to give the expected Te(IV) halogenated products bis[2-(phenylazo)phenyl-C, N′]tellurium(IV) dichloride (13) and bis[2-(phenylazo)phenyl-C,N′] tellurium(IV) dibromide (11), respectively. However, a similar reaction of 10 with I2 resulted in the formation of an unexpected telluronium cation, iodobis[2-(phenylazo)phenyl-C,N′]telluronium triiodide (14), and [2-(phenylazo)phenyl-C,N′]tellurenenyl(II) iodide (12). Alkaline hydrolysis of 16 under reflux conditions resulted in the formation of monomeric [2-(phenylazo)phenyl-C,N′]tellurinic acid (20) and its sodium salt (21) as a cocrystal. Bis[[2-(phenylazo)phenyl-C,N′]tellurium]oxide (22) was obtained from the hydrolysis of [2-(phenylazo)phenyl-C,N′]tellurium(II) chloride (17). The reaction of 13 with an alkaline solution resulted in the formation of the corresponding bis[2-(phenylazo)phenyl-C,N′]tellurium(IV) oxide (23) and dichlorobis[2-(phenylazo)phenyl-C,N′]tellurium(IV) oxide (24). The identity of all the derivatives was confirmed by multinuclear NMR (1H, 13C, 125Te) and FT-IR spectroscopy, elemental analysis, and ESI-MS. The structures for tellurium derivatives 6, 10-14, 17, 19, 20-23, and 23A were also confirmed by X-ray crystallography. Density functional theory (DFT) was utilized for optimizing the geometries of 11, 13, and 14 to examine the possibility of a four-membered intramolecular Te⋯N interaction.
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U2 - 10.1021/om1009022
DO - 10.1021/om1009022
M3 - Article
AN - SCOPUS:79751491695
SN - 0276-7333
VL - 30
SP - 534
EP - 546
JO - Organometallics
JF - Organometallics
IS - 3
ER -