2013
DOI: 10.1039/c2dt32716c
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A planar dianionic ditelluride and a cyclic tritelluride supported by P2N2rings

Abstract: with a planar P 6 E 6 (E = S, Se) framework in which dichalcogenido (-E-E-) groups are linked by perpendicular 20 P V 2 N 2 rings. 5 The synthesis of these polychalcogen macrocycles involves the two-electron oxidation of the dianions 1a and 1b with I 2. We now report a detailed investigation of the oxidation of the tellurium analogue 1c that provides important insights into the initial oxidation process, as well as a notable difference in the 25 final outcome of the oxidation compared to that observed for 1a a… Show more

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Cited by 26 publications
(24 citation statements)
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“…As depicted in Fig. 7 Although it is highly insoluble in common solvents, microtubular tellurium crystals can be grown from ethylenediamine; 10a hexagonal grey tellurium is also very soluble in a thiol-amine solvent mixture, presumably because the intermolecular contacts are disrupted in these solvents.…”
Section: General Bonding Featuresmentioning
confidence: 99%
“…As depicted in Fig. 7 Although it is highly insoluble in common solvents, microtubular tellurium crystals can be grown from ethylenediamine; 10a hexagonal grey tellurium is also very soluble in a thiol-amine solvent mixture, presumably because the intermolecular contacts are disrupted in these solvents.…”
Section: General Bonding Featuresmentioning
confidence: 99%
“…[20][21][22][23][24][25][26][27][28][29] Of particular interest is the pentameric host macrocycle 1 (Figure 1), toroidal shape,l arge void volume, endo-cyclic N-H functionalities,a nd exo-cyclic t Bu groups of which make it ahighly unusual, sterically hindered H-bonding host. [20][21][22][23][24][25][26][27][28][29] Of particular interest is the pentameric host macrocycle 1 (Figure 1), toroidal shape,l arge void volume, endo-cyclic N-H functionalities,a nd exo-cyclic t Bu groups of which make it ahighly unusual, sterically hindered H-bonding host.…”
mentioning
confidence: 99%
“…[17][18][19] Key advantages of inorganic anion receptors over organic counterparts are their inherently more polar nature and the ease by which their proton acidities can be modulated.Thehigh bond energy of PÀNs ingle bonds and their low polarity underpin the stability of adiverse range of previously reported phosphazane compounds,and provide agood foundation for the development of anew range of robust inorganic macrocycles. [20][21][22][23][24][25][26][27][28][29] Of particular interest is the pentameric host macrocycle 1 (Figure 1), toroidal shape,l arge void volume, endo-cyclic N-H functionalities,a nd exo-cyclic t Bu groups of which make it ahighly unusual, sterically hindered H-bonding host. Thehost properties of 1 should differ significantly from organic counterparts,e specially given the greater polarity of these P À N-bonded frameworks.Herein, we show that the highly polar nature of the binding site and the sterically congested periphery of 1 leads to unique types of host-guest binding involving NÀH···p-CX (X = CH, N, P) hydrogen bonding to organic and inorganic guests.W ea lso show that oxidation of the phosphorus periphery of 1 can be used to kinetically entrap anions within the macrocycle.T his produces chemically irreversible binding of Cl À and I À anions using acombination of hydrogen bonding and steric encasement, which results in better effective binding of these halides than in any organic or metal-organic architecture.Direct access to 1,w hich was previously prepared by ac omplicated two-step procedure involving the use of gaseous NH 3 ,i sp rovided here by an ew method wherein the cyclodiphosphazane [ClP(m-N t Bu)] 2 (A)iscombined with LiNH 2 in the presence of excess anhydrous LiI, followed by removal of the encapsulated iodide anion (Figure 2a and Section S2 in the Supporting Information).…”
mentioning
confidence: 99%
“…Two intermediates have been isolated and structurally characterized, viz. the planar dianionic ditelluride 66 183 and the spirocyclic dianion 67 with a central Te 5 motif (Figure 31). 187 The final product is the cyclic tritelluride 68 ( Figure 30).…”
Section: Scheme 12 Synthesis Of Metal Complexes Of Telluroimidophospmentioning
confidence: 99%
“…187 The final product is the cyclic tritelluride 68 ( Figure 30). 183 The complex [Li(TMEDE)] 2 66 is a rare example of a planar ditelluride. In this case, the planarity is attributed to packing effects, 183 however a planar conformation may also be imposed either by very bulky substituents or via intramolecular heteroatom-tellurium interactions.…”
Section: Scheme 12 Synthesis Of Metal Complexes Of Telluroimidophospmentioning
confidence: 99%