Experimental and theoretical investigations of the contact Ion pairs formed by reactions of the anions [(EPR2)(2)N](-) (R = Pr-i, Bu-t; E = S, Se) with the cations [(TePR2)(2)N](+) (R = Pr-i, Bu-t)

Stuart D. Robertson, Tristram Chivers, Heikki M. Tuononen

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Abstract

Reactions of the sodium salts [(EPR2)(2)N]Na(TMEDA) (R = Pr-i, Bu-t; E = S, Se) with the iodide salts [(TePR2)(2)N]l (R = Pr-i, Bu-t) in toluene produce the mixed-chalcogen systems [(EPR2)(2)N][(TePR2)(2)N] (6b, E = Se, R = Bu-t; 6c, E = S, R = Bu-t; 7b, E = Se, R = Pr-i; 7c, E = S, R = Pr-i). Compounds 6b, 6c, 7b, and 7c have been characterized in solution by variable-temperature multinuclear (P-31, Se-77, and Te-125) NMR spectroscopy and in the solid state by single-crystal X-ray crystallography. The structures are comprised of contact ion pairs linked by bonds between Te and S or Se atoms. For the tert-butyl derivatives 6b and 6c, the anionic half of the molecule is coordinated in a bidentate (E,E') fashion to one Te atom of the cationic half to give a spirocycle, whereas in the isopropyl derivatives 7b and 7c, the anion acts as a monodentate ligand with only one E-Te bond and the second S or Se atom pointing away from the cation. A comparison of the chalcogen-chalcogen bond orders in 6b, 6c, and the all-tellurium system 6a (E = Te), as determined from the experimental bond lengths, shows that the Te-Te bond order in the cations decreases as the strength of the E-Te interaction increases. This trend is attributed to increased electron donation from the anion into the lowest unoccupied molecular orbital [sigma*(Te-Te)] of the cation along the series S < Se < Te. A similar trend is observed for the monodentate contact ion pairs 7b and 7c. Density functional theory calculations provided information about the relative energies of bidentate and monodentate contact ion pair structures and the extent of intramolecular electron transfer in these systems.

LanguageEnglish
Pages6755-6762
Number of pages8
JournalInorganic Chemistry
Volume48
Issue number14
Early online date26 May 2009
DOIs
Publication statusPublished - 20 Jul 2009

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Chalcogens
Anions
Cations
Ions
anions
cations
Atoms
Salts
Tellurium
salts
Derivatives
atoms
trends
ions
Electrons
X ray crystallography
Toluene
Bond length
Iodides
Molecular orbitals

Keywords

  • chemical-vapor-deposition
  • single-source-precursors
  • X-ray structures
  • imino-bis(diisopropylphosphine chalcogenide) complexes
  • selenide thin-films
  • metal-complexes
  • coordination chemistry
  • crystal-structures
  • indium selenide
  • e-unidentate

Cite this

@article{4e0b40a5cec349f4a2d42b0988b7cc44,
title = "Experimental and theoretical investigations of the contact Ion pairs formed by reactions of the anions [(EPR2)(2)N](-) (R = Pr-i, Bu-t; E = S, Se) with the cations [(TePR2)(2)N](+) (R = Pr-i, Bu-t)",
abstract = "Reactions of the sodium salts [(EPR2)(2)N]Na(TMEDA) (R = Pr-i, Bu-t; E = S, Se) with the iodide salts [(TePR2)(2)N]l (R = Pr-i, Bu-t) in toluene produce the mixed-chalcogen systems [(EPR2)(2)N][(TePR2)(2)N] (6b, E = Se, R = Bu-t; 6c, E = S, R = Bu-t; 7b, E = Se, R = Pr-i; 7c, E = S, R = Pr-i). Compounds 6b, 6c, 7b, and 7c have been characterized in solution by variable-temperature multinuclear (P-31, Se-77, and Te-125) NMR spectroscopy and in the solid state by single-crystal X-ray crystallography. The structures are comprised of contact ion pairs linked by bonds between Te and S or Se atoms. For the tert-butyl derivatives 6b and 6c, the anionic half of the molecule is coordinated in a bidentate (E,E') fashion to one Te atom of the cationic half to give a spirocycle, whereas in the isopropyl derivatives 7b and 7c, the anion acts as a monodentate ligand with only one E-Te bond and the second S or Se atom pointing away from the cation. A comparison of the chalcogen-chalcogen bond orders in 6b, 6c, and the all-tellurium system 6a (E = Te), as determined from the experimental bond lengths, shows that the Te-Te bond order in the cations decreases as the strength of the E-Te interaction increases. This trend is attributed to increased electron donation from the anion into the lowest unoccupied molecular orbital [sigma*(Te-Te)] of the cation along the series S < Se < Te. A similar trend is observed for the monodentate contact ion pairs 7b and 7c. Density functional theory calculations provided information about the relative energies of bidentate and monodentate contact ion pair structures and the extent of intramolecular electron transfer in these systems.",
keywords = "chemical-vapor-deposition, single-source-precursors, X-ray structures, imino-bis(diisopropylphosphine chalcogenide) complexes, selenide thin-films, metal-complexes, coordination chemistry, crystal-structures, indium selenide, e-unidentate",
author = "Robertson, {Stuart D.} and Tristram Chivers and Tuononen, {Heikki M.}",
year = "2009",
month = "7",
day = "20",
doi = "10.1021/ic900703e",
language = "English",
volume = "48",
pages = "6755--6762",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "14",

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TY - JOUR

T1 - Experimental and theoretical investigations of the contact Ion pairs formed by reactions of the anions [(EPR2)(2)N](-) (R = Pr-i, Bu-t; E = S, Se) with the cations [(TePR2)(2)N](+) (R = Pr-i, Bu-t)

AU - Robertson, Stuart D.

AU - Chivers, Tristram

AU - Tuononen, Heikki M.

PY - 2009/7/20

Y1 - 2009/7/20

N2 - Reactions of the sodium salts [(EPR2)(2)N]Na(TMEDA) (R = Pr-i, Bu-t; E = S, Se) with the iodide salts [(TePR2)(2)N]l (R = Pr-i, Bu-t) in toluene produce the mixed-chalcogen systems [(EPR2)(2)N][(TePR2)(2)N] (6b, E = Se, R = Bu-t; 6c, E = S, R = Bu-t; 7b, E = Se, R = Pr-i; 7c, E = S, R = Pr-i). Compounds 6b, 6c, 7b, and 7c have been characterized in solution by variable-temperature multinuclear (P-31, Se-77, and Te-125) NMR spectroscopy and in the solid state by single-crystal X-ray crystallography. The structures are comprised of contact ion pairs linked by bonds between Te and S or Se atoms. For the tert-butyl derivatives 6b and 6c, the anionic half of the molecule is coordinated in a bidentate (E,E') fashion to one Te atom of the cationic half to give a spirocycle, whereas in the isopropyl derivatives 7b and 7c, the anion acts as a monodentate ligand with only one E-Te bond and the second S or Se atom pointing away from the cation. A comparison of the chalcogen-chalcogen bond orders in 6b, 6c, and the all-tellurium system 6a (E = Te), as determined from the experimental bond lengths, shows that the Te-Te bond order in the cations decreases as the strength of the E-Te interaction increases. This trend is attributed to increased electron donation from the anion into the lowest unoccupied molecular orbital [sigma*(Te-Te)] of the cation along the series S < Se < Te. A similar trend is observed for the monodentate contact ion pairs 7b and 7c. Density functional theory calculations provided information about the relative energies of bidentate and monodentate contact ion pair structures and the extent of intramolecular electron transfer in these systems.

AB - Reactions of the sodium salts [(EPR2)(2)N]Na(TMEDA) (R = Pr-i, Bu-t; E = S, Se) with the iodide salts [(TePR2)(2)N]l (R = Pr-i, Bu-t) in toluene produce the mixed-chalcogen systems [(EPR2)(2)N][(TePR2)(2)N] (6b, E = Se, R = Bu-t; 6c, E = S, R = Bu-t; 7b, E = Se, R = Pr-i; 7c, E = S, R = Pr-i). Compounds 6b, 6c, 7b, and 7c have been characterized in solution by variable-temperature multinuclear (P-31, Se-77, and Te-125) NMR spectroscopy and in the solid state by single-crystal X-ray crystallography. The structures are comprised of contact ion pairs linked by bonds between Te and S or Se atoms. For the tert-butyl derivatives 6b and 6c, the anionic half of the molecule is coordinated in a bidentate (E,E') fashion to one Te atom of the cationic half to give a spirocycle, whereas in the isopropyl derivatives 7b and 7c, the anion acts as a monodentate ligand with only one E-Te bond and the second S or Se atom pointing away from the cation. A comparison of the chalcogen-chalcogen bond orders in 6b, 6c, and the all-tellurium system 6a (E = Te), as determined from the experimental bond lengths, shows that the Te-Te bond order in the cations decreases as the strength of the E-Te interaction increases. This trend is attributed to increased electron donation from the anion into the lowest unoccupied molecular orbital [sigma*(Te-Te)] of the cation along the series S < Se < Te. A similar trend is observed for the monodentate contact ion pairs 7b and 7c. Density functional theory calculations provided information about the relative energies of bidentate and monodentate contact ion pair structures and the extent of intramolecular electron transfer in these systems.

KW - chemical-vapor-deposition

KW - single-source-precursors

KW - X-ray structures

KW - imino-bis(diisopropylphosphine chalcogenide) complexes

KW - selenide thin-films

KW - metal-complexes

KW - coordination chemistry

KW - crystal-structures

KW - indium selenide

KW - e-unidentate

U2 - 10.1021/ic900703e

DO - 10.1021/ic900703e

M3 - Article

VL - 48

SP - 6755

EP - 6762

JO - Inorganic Chemistry

T2 - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 14

ER -