New insights into the chemistry of imidodiphosphinates from investigations of tellurium-centered systems

Tristram Chivers, Jamie S. Ritch, Stuart D. Robertson, Jari Konu, Heikki M. Tuononen

Research output: Contribution to journalLiterature review

48 Citations (Scopus)

Abstract

Dichalcogenido-imidodiphosphinates, [N(PR2E)(2)](-) (R = alkyl, aryl), are chelating ligands that readily form cyclic complexes with main group metals, transition metals, lanthanides, and actinides. Since their discovery in the early 1960s, researchers have studied the structural chemistry of the resulting metal complexes (where E = O, S, Se) extensively and identified a variety of potential applications, including as NMR shift reagents, luminescent complexes in photonic devices, or single-source precursors for metal sulfides or selenides. In 2002, a suitable synthesis of the tellurium analogs [N(PR2Te)(2)](-) was developed. In this Account, we describe comprehensive investigations of the chemistry of these tellurium-centered anions, and related mixed chalcogen systems, which have revealed unanticipated features of their fundamental structure and reactivity.

An exhaustive examination of previously unrecognized redox behavior has uncovered a variety of novel dimeric arrangements of these ligands, as well as an extensive series of cyclic cations. In combination with calculations using density functional theory, these new structural frameworks have provided new insights into the nature of chalcogen-chalcogen bonding. Studies of metal complexes of the ditellurido ligands [N(PR2Te)(2)](-) have revealed unprecedented structural and reaction chemistry. The large tellurium donor sites confer greater flexibility, which can lead to unique structures in which the tellurium-centered ligand bridges two metal centers. The relatively weak P-Te bonds facilitate metal-insertion reactions (intramolecular oxidative-addition) to give new metal tellurium ring systems for some group 11 and 13 metals. Metal tellurides have potential applications as low band gap semiconductor materials in solar cells, thermoelectric devices, and in telecommunications. Practically, some of these telluride ligands could be applied in these industries. For example, certain metal complexes of the isopropyl-substituted anion [N((PPr2Te)-Pr-I)(2)](-) serve as suitable single-source precursors for pure metal telluride thin films or novel nanomaterials, for example, CdTe, PbTe, In2Te3, and Sb2Te3.

LanguageEnglish
Pages1053-1062
Number of pages10
JournalAccounts of Chemical Research
Volume43
Issue number8
DOIs
Publication statusPublished - Aug 2010

Fingerprint

Tellurium
Metals
Chalcogens
Ligands
Coordination Complexes
Anions
Actinoid Series Elements
Lanthanoid Series Elements
Photonic devices
Sulfides
Chelation
Nanostructured materials
Transition metals
Telecommunication
Density functional theory
Cations
Solar cells
Energy gap
Nuclear magnetic resonance
Semiconductor materials

Keywords

  • chemical vapor deposition
  • single source precursors
  • x-ray structures
  • contact ion-pairs
  • thin films
  • crystal structures

Cite this

Chivers, Tristram ; Ritch, Jamie S. ; Robertson, Stuart D. ; Konu, Jari ; Tuononen, Heikki M. / New insights into the chemistry of imidodiphosphinates from investigations of tellurium-centered systems. In: Accounts of Chemical Research . 2010 ; Vol. 43, No. 8. pp. 1053-1062.
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New insights into the chemistry of imidodiphosphinates from investigations of tellurium-centered systems. / Chivers, Tristram; Ritch, Jamie S.; Robertson, Stuart D.; Konu, Jari; Tuononen, Heikki M.

In: Accounts of Chemical Research , Vol. 43, No. 8, 08.2010, p. 1053-1062.

Research output: Contribution to journalLiterature review

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T1 - New insights into the chemistry of imidodiphosphinates from investigations of tellurium-centered systems

AU - Chivers, Tristram

AU - Ritch, Jamie S.

AU - Robertson, Stuart D.

AU - Konu, Jari

AU - Tuononen, Heikki M.

PY - 2010/8

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N2 - Dichalcogenido-imidodiphosphinates, [N(PR2E)(2)](-) (R = alkyl, aryl), are chelating ligands that readily form cyclic complexes with main group metals, transition metals, lanthanides, and actinides. Since their discovery in the early 1960s, researchers have studied the structural chemistry of the resulting metal complexes (where E = O, S, Se) extensively and identified a variety of potential applications, including as NMR shift reagents, luminescent complexes in photonic devices, or single-source precursors for metal sulfides or selenides. In 2002, a suitable synthesis of the tellurium analogs [N(PR2Te)(2)](-) was developed. In this Account, we describe comprehensive investigations of the chemistry of these tellurium-centered anions, and related mixed chalcogen systems, which have revealed unanticipated features of their fundamental structure and reactivity. An exhaustive examination of previously unrecognized redox behavior has uncovered a variety of novel dimeric arrangements of these ligands, as well as an extensive series of cyclic cations. In combination with calculations using density functional theory, these new structural frameworks have provided new insights into the nature of chalcogen-chalcogen bonding. Studies of metal complexes of the ditellurido ligands [N(PR2Te)(2)](-) have revealed unprecedented structural and reaction chemistry. The large tellurium donor sites confer greater flexibility, which can lead to unique structures in which the tellurium-centered ligand bridges two metal centers. The relatively weak P-Te bonds facilitate metal-insertion reactions (intramolecular oxidative-addition) to give new metal tellurium ring systems for some group 11 and 13 metals. Metal tellurides have potential applications as low band gap semiconductor materials in solar cells, thermoelectric devices, and in telecommunications. Practically, some of these telluride ligands could be applied in these industries. For example, certain metal complexes of the isopropyl-substituted anion [N((PPr2Te)-Pr-I)(2)](-) serve as suitable single-source precursors for pure metal telluride thin films or novel nanomaterials, for example, CdTe, PbTe, In2Te3, and Sb2Te3.

AB - Dichalcogenido-imidodiphosphinates, [N(PR2E)(2)](-) (R = alkyl, aryl), are chelating ligands that readily form cyclic complexes with main group metals, transition metals, lanthanides, and actinides. Since their discovery in the early 1960s, researchers have studied the structural chemistry of the resulting metal complexes (where E = O, S, Se) extensively and identified a variety of potential applications, including as NMR shift reagents, luminescent complexes in photonic devices, or single-source precursors for metal sulfides or selenides. In 2002, a suitable synthesis of the tellurium analogs [N(PR2Te)(2)](-) was developed. In this Account, we describe comprehensive investigations of the chemistry of these tellurium-centered anions, and related mixed chalcogen systems, which have revealed unanticipated features of their fundamental structure and reactivity. An exhaustive examination of previously unrecognized redox behavior has uncovered a variety of novel dimeric arrangements of these ligands, as well as an extensive series of cyclic cations. In combination with calculations using density functional theory, these new structural frameworks have provided new insights into the nature of chalcogen-chalcogen bonding. Studies of metal complexes of the ditellurido ligands [N(PR2Te)(2)](-) have revealed unprecedented structural and reaction chemistry. The large tellurium donor sites confer greater flexibility, which can lead to unique structures in which the tellurium-centered ligand bridges two metal centers. The relatively weak P-Te bonds facilitate metal-insertion reactions (intramolecular oxidative-addition) to give new metal tellurium ring systems for some group 11 and 13 metals. Metal tellurides have potential applications as low band gap semiconductor materials in solar cells, thermoelectric devices, and in telecommunications. Practically, some of these telluride ligands could be applied in these industries. For example, certain metal complexes of the isopropyl-substituted anion [N((PPr2Te)-Pr-I)(2)](-) serve as suitable single-source precursors for pure metal telluride thin films or novel nanomaterials, for example, CdTe, PbTe, In2Te3, and Sb2Te3.

KW - chemical vapor deposition

KW - single source precursors

KW - x-ray structures

KW - contact ion-pairs

KW - thin films

KW - crystal structures

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