PI and PIII Ions Supported by BZIMPY Ligands

Author:

LaFortune James H. W.1,Swidan Ala'aeddeen2,Ovens Jeffrey S.3,Qu Zheng‐Wang4,Grimme Stefan4,Land Michael A.5,Macdonald Charles L. B.125ORCID

Affiliation:

1. Department of Chemistry Carleton University 1125 Colonel By Drive Ottawa Ontario K1S 5B6 Canada

2. Department of Chemistry and Biochemistry University of Windsor 401 Sunset Ave. Windsor Ontario N9B 3P4 Canada

3. Department of Chemistry and Biomolecular Sciences University of Ottawa 150 Louis-Pasteur Ottawa Ontario K1 N 6 N5 Canada

4. Mulliken Center for Theoretical Chemistry Clausius Institut für Physikalische und Theoretische Chemie Rheinische Friedrich-Wilhelms-Universität Bonn Beringstrasse 4 53115 Bonn Germany

5. Department of Chemistry Dalhousie University Halifax Nova Scotia B3H 4 J3 Canada

Abstract

AbstractWe report a class of compounds in which both PIII−X and PI forms featuring the same ligand are stable and readily cycled with each other. A series of PIII−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 R3PO (R=Et, Oct) results in reduction to BZIMPY‐ligated PI monocationic triflate salts while treatment with Ph3P reduces but also substitutes the compound to produce Ph3P‐BZIMPY‐ligated PI dicationic triflate salts. The mechanisms of these surprising reductions are probed experimentally and rationalized computationally. The PIII−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 PI mono‐ and dications are shown to be very effective P+ transfer agents when treated similarly. Oxidation from a monocationic PI salt back to the dicationic PIII−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.

Funder

Natural Sciences and Engineering Research Council of Canada

Deutsche Forschungsgemeinschaft

Publisher

Wiley

Subject

General Chemistry,Catalysis,Organic Chemistry

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