Iodenium or Phosphonium: The Ambi-Valent Character of Iodophosphonium Complexes
| Autor: | Kevin Basemann, Kathleen M. Riley, Jennifer J. Becker, Michel R. Gagné |
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| Rok vydání: | 2022 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry. 61:17550-17556 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.2c02543 |
| Popis: | The ambi-valent character of the P-I bond in iodophosphonium complexes ensures that it can be electrophilic at either P or I. Herein, we use an ensemble of computational tools and methodologies to probe the nature of this ambi-valent bond. Geometric and atomic electron population analyses yielded strong trends between the electron donating ability of the phosphine and the strength and polarity of the P-I bond. Quasi-atomic orbital analysis demonstrated the near homo-polarity of the P-I bond, and energy decomposition analysis calculations demonstrated the ability to tune the polarization of the bond with only mild changes in secondary structural features. Finally, the ambi-valent nature of the P-I bond was demonstrated to follow hard-soft considerations in reactions with nucleophiles, with harder nucleophiles preferentially forming products of addition to P and softer nucleophiles to I. |
| Databáze: | OpenAIRE |
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