Secondary bonding. Part 13. Aryl-tellurium(IV) and -iodine(III) acetates and trifluoroacetates. The crystal and molecular structures of bis-(p-methoxyphenyl)tellurium diacetate, µ-oxo-bis[diphenyltrifluoroacetoxytellurium] hydrate, and [bis(trifluoroacetoxy)iodo]benzene

Abstract

p-met hoxy p hen y I ) t el I u r i u m D iacet at e, p -0 x 0 = b is [ d i p hen y I t r if 1 u or0 -acetoxytellurium] Hydrate, and [ Bis(trif luoroacetoxy)iodo] benzene tThe crystal and molecular structures of the title compounds have been determined from diffractometer data by the heavy-atom method, and their preparations are described. Crystals of (p-MeOC6H4)2Te(02CMe)2 (1 ) are monoclinic, space group P2, fc, with unit-cell dimensions a = 9.529(2), b = 11.984(2), c = 17.035(2) A, p = lOl.i0(2)", 2 = 4, and for 3 033 observed reflections [ l / o ( l ) > 3.01, R = 0.022. Crystals of ([Ph2Te(02CCF3)]20)2*H20 (2) are triclinic, space group P7, with unit-cell dimensions a = 13.988 (3), b = 14.287(3), c = 15.689(3) A, cc = 80.40(2), 6 = 81.89(2), y = 86.65(2)", Z = 2, and for 5 290 observed reflections, R = 0.042.a Crystals of Phl(02CCF3)2 (3) are triclinic, space group P i , with unit-cell dimensions a = 9.787(4), b = 9.055(3), c = 7.674(3) A, a = 91.45(3), p = 99.78(3), y = 89.21 (3)", Z = 2, and for 2 104 observed reflections, R = 0.037. All three compounds have pseudo-trigonalbipyramidal primary geometry [Te-C 2.098(3) and 2.1 03(4), I-C 2.074(4) ; Te-O(p-0x0) 1.981 (7), Te-0 and 1-0 (oxy-anion) 2.1 38-2.352 A], and form secondary bonds to give pentagonal planar systems around Te and I, also with linear C-Te 0 systems. In the light of these results, previously published tellurium nitrate structures are re-interpreted.We have previously examined the intra-and inter-molecular bonding in phenyliodine acetate, dichloroacetate, and nitrate,, and in several phenyltellurium nitrate^.^ These have revealed a diversity of bonding patterns, markedly more complex than those found in the corresponding haiides.'~~ Both series of oxy-salts include an alternation between 'neutral* salts, e.g. PhI(02CMe), and PhZTe(ON02),, and p-0x0-salts, e.g. PhI(ON0,)-0-I(ON0,)Ph. For the iodine compounds, a pattern has also been recognised of 'pentagonal planar' co-ordination, combining the T-shaped geometry expected for iodine(1n) with two secondary I 0 bonds, e.g. structure (A). Nothing similar has yet been recognised in the tellurium compounds. In this paper, additional evidence is brought to bear, from the structures of an aryltellurium acetate and trifluoroacetates of both tellurium and iodine. ExperimentalPreparations.---(p-MeOC6H4),Te(02C Me)2, Compound ( 1 ). Tellurium tetrachloride (27 g, 0.1 mol) was dissolved in a slight excess of anisole (25 cm3, 0.23 m~l ) .~The yellow solution soon became orange and HCI was evolved [reaction (i)]. The solution was then gradually warmed (3 h) to about 100°C until HCI evolution ceased and a solid red-brown mass of the crude product remained. This was recrystallised several times from methanol in the presence of charcoal, until colourless crystals of (p-MeOC6H4)27ieClz were obtained. This compound (0.41 g, 1 mmol) was then dissolved in benzene and AgOzCMe added (0.35 g, 2.1 mmol). The mixture was stirred under reflux for 3 h, filtered, and evaporated slowly to give large crystals of (p-MeOC6H4)2...

Supramolecular Aggregation of Perfluoroorganyl Iodane Reagents in the Solid State and in Solution

“…code ABZIOX) and PhI(OOCCF 3 ) 2 (CSD ref. code CEZBEO01) . Regardless of the coordination mode of the COO group, the secondary I ··· O interactions lead to the formation of supramolecular polymeric chains in all acid‐type iodane reagents (Figure a).…”

Trifluoromethyl Derivatives of Benzooxatellurole

“…For example, compounds of general structure A were prepared by Wada, [4] Beckmann, [5] Takaguchi, [6] and Alcock. [7] The structural motif of a five-membered ring containing a tellurium (IV) center coordinated by an oxygen, a halide, and a carbon ligand (type B) was reported by Sadekov, Minkin, [8][9][10] and later by Kaizumi. [11][12][13] Preparation of type C compounds was first reported by Sadekov, Minkin, and coworkers.…”

Hypervalent aryliodine compounds as precursors for radiofluorination

“…The strong bonds between the central iodine atom to a carbon atom of the phenyl group and to one oxygen atom of each carboxylate group plus 2 secondary bonds to the 2 remaining oxygen atoms give an overall pentagonal‐planar bonding arrangement (Figure ). The simple trifluoroacetoxy analog [PhI(CF 3 CO 2 ) 2 ; PIFA] exists as a bridged dimer in the solid state …”

“…The simple trifluoroacetoxy analog [PhI(CF 3 CO 2 ) 2 ; PIFA] exists as a bridged dimer in the solid state. 28…”