التفاصيل البيبلوغرافية
| العنوان: |
P I and P III Ions Supported by BZIMPY Ligands |
| المؤلفون: |
LaFortune, James H. W., Swidan, Ala'aeddeen, Ovens, Jeffrey S., Qu, Zheng‐Wang, Grimme, Stefan, Land, Michael A., Macdonald, Charles L. B. |
| المساهمون: |
Natural Sciences and Engineering Research Council of Canada, Deutsche Forschungsgemeinschaft |
| المصدر: |
Chemistry – A European Journal ; volume 29, issue 70 ; ISSN 0947-6539 1521-3765 |
| بيانات النشر: |
Wiley |
| سنة النشر: |
2023 |
| المجموعة: |
Wiley Online Library (Open Access Articles via Crossref) |
| الوصف: |
We report a class of compounds in which both P III −X and P I forms featuring the same ligand are stable and readily cycled with each other. A series of P III −X (X=Cl, Br, I) dicationic triflate salts supported by benzyl‐ and allyl‐substituted 2,6‐bis(benzimidazole‐2‐yl)pyridine (BZIMPY) ligands is synthesized. Surprisingly, treatment of these with R 3 PO (R=Et, Oct) results in reduction to BZIMPY‐ligated P I monocationic triflate salts while treatment with Ph 3 P reduces but also substitutes the compound to produce Ph 3 P‐BZIMPY‐ligated P I dicationic triflate salts. The mechanisms of these surprising reductions are probed experimentally and rationalized computationally. The P III −X dications are shown to be strong Lewis acids both experimentally and computationally and to readily behave as X + , PX, and P + transfer agents in reactions with phosphines, NHCs, and diazabutadienes. The P I mono‐ and dications are shown to be very effective P + transfer agents when treated similarly. Oxidation from a monocationic P I salt back to the dicationic P III −X (X=Cl, Br) salt was achieved by treatment with N‐chlorosuccinimide (NCS) or N‐bromosuccinimide (NBS). Full characterization is reported using multinuclear nuclear magnetic resonance spectroscopy, elemental analysis, and single‐crystal X‐ray diffractometry where suitable crystals were isolated. |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
English |
| DOI: |
10.1002/chem.202302558 |
| الإتاحة: |
https://doi.org/10.1002/chem.202302558Test |
| حقوق: |
http://creativecommons.org/licenses/by-nc-nd/4.0Test/ |
| رقم الانضمام: |
edsbas.8EC1552D |
| قاعدة البيانات: |
BASE |
