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New Insights into the Chemistry of Imidodiphosphinates from Investigations of Tellurium-Centered Systems

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Chivers, T., Ritch, J., Robertson, S., Konu, J., & Tuononen, H. (2010). New Insights into the Chemistry of Imidodiphosphinates from Investigations of Tellurium-Centered Systems. Accounts of Chemical Research, 43(8), 1053-1062. https://doi.org/10.1021/ar900272k
Published in
Accounts of Chemical Research
Authors
Chivers, Tristram |
Ritch, Jamie |
Robertson, Stuart |
Konu, Jari |
Tuononen, Heikki
Date
2010
Discipline
Epäorgaaninen ja analyyttinen kemiaInorganic and Analytical Chemistry
Copyright
© 2010 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.

 
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(PiPr2Te)2]− serve as suitable single-source precursors for pure metal telluride thin films or novel nanomaterials, for example, CdTe, PbTe, In2Te3, and Sb2Te3. ...
Publisher
ACS
ISSN Search the Publication Forum
0001-4842
Keywords
imidodifosfinaatit imidodiphosphinates
DOI
https://doi.org/10.1021/ar900272k
URI

http://urn.fi/URN:NBN:fi:jyu-201511203748

Publication in research information system

https://converis.jyu.fi/converis/portal/detail/Publication/20144130

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