Experimental and Theoretical Investigations of the Redox Behavior of the Heterodichalcogenido Ligands [(EPiPr2)(TePiPr2)N]−(E = S, Se): Cyclic Cations and Acyclic Dichalcogenide Dimers
Abstract:The two-electron oxidation of the lithium salts of the heterodichalcogenidoimidodiphosphinate anions [(EP i Pr 2 )(TeP i Pr 2 )N] -(1a, E ) S; 1b, E ) Se) with iodine yields cyclic cations [(EP i Pr 2 )(TeP i Pr 2 )N] + as their iodide salts [(SP i Pr 2 )(TeP i Pr 2 )N]I (2a) and [(SeP i Pr 2 )(TeP i Pr 2 )N]I (2b). The five-membered rings in 2a and 2b both display an elongated E-Te bond as a consequence of an interaction between tellurium and the iodide anion. Oneelectron reduction of 2a and 2b with cobaltoce… Show more
“…As noted earlier, the known heterodichalcogenide dimers are exclusively obtained as ditellurides. 38 However, it is not as straightforward to rationalize why 7b and 7c adopt a monodentate coordination mode.…”
Section: Theoretical Investigations Of Structural Isomers Of 6 Andmentioning
confidence: 99%
“…36,37 For the heterodichalcogenidoimidodiphosphinate (2, E ≠ E′), the resulting dimer is exclusively obtained as a ditelluride with a Te-Te interaction rather than an E-E or E-Te interaction. 38 The second bonding mode is best described as a spirocyclic contact ion pair (5) in which a dichalcogenido anion is chelated to one of the chalcogen atoms of the corresponding cation. 37 To date this structural type has been limited to the all-tellurium system with R = t Bu.…”
“…As noted earlier, the known heterodichalcogenide dimers are exclusively obtained as ditellurides. 38 However, it is not as straightforward to rationalize why 7b and 7c adopt a monodentate coordination mode.…”
Section: Theoretical Investigations Of Structural Isomers Of 6 Andmentioning
confidence: 99%
“…36,37 For the heterodichalcogenidoimidodiphosphinate (2, E ≠ E′), the resulting dimer is exclusively obtained as a ditelluride with a Te-Te interaction rather than an E-E or E-Te interaction. 38 The second bonding mode is best described as a spirocyclic contact ion pair (5) in which a dichalcogenido anion is chelated to one of the chalcogen atoms of the corresponding cation. 37 To date this structural type has been limited to the all-tellurium system with R = t Bu.…”
“…158 This protocol is also the preferred procedure for the preparation of lithium derivatives of the mixed-chalcogen anions [N(P i Pr 2 E)(P i Pr 2 + with cobaltocene. 160 The related mixedchalcogen systems Cp 2 Co[N(P i Pr 2 E)(P i Pr 2 Te)] are prepared by using a similar synthetic protocol. …”
Section: Tellurophosphinites and Ditellurophosphinatesmentioning
“…DFT towards the more electropositive tellurium atom when E = S, Se resulting in stronger TeTe overlap. 11 The elongation of the central chalcogen-chalcogen bond in the diselenides 4b and 4b ′ is ca. 6 % and that in the disulfide 4c′ is only 2 %, suggesting better overlap of the two radical SOMOs for the lighter chalcogens We note, however, that the markedly different conformations of acyclic DCs is likely to be a contributing factor.…”
Section: Redox Behaviormentioning
confidence: 99%
“…13 The mixed chalcogen systems 6c and 6d are prepared in a similar manner. 11 The hexafluoroantimonate salts 7a,b are produced by metathesis of the corresponding iodide salts with Ag[SbF6] (Scheme 2). 14 The salts 6a and 6b are comprised of a five-membered cyclic cation [N(P i Pr2E)2] + and an iodide counterion that interacts with one of the chalcogens to form an infinite chain structure (Figure 2).…”
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