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We 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. [ABSTRACT FROM AUTHOR]

Treatment of two equivalents of the triphosphenium zwitterion L with sources of Ni0 and Pd0 form the mononuclear η2‐diphosphoniodiphosphene complexes 1 and 2. The reaction between L and [FeCp(CO)2]2 results in the binuclear μ‐η1:η1‐diphosphoniodiphosphene iron complex 3, which features an alternative bonding motif of the diphosphoniodiphosphene unit. The formation of these species has been confirmed by spectroscopic methods and single‐crystal X‐ray diffraction analysis, and their electronic structures have been elucidated using computational methods. A diphosphoniodiphosphene is unexpectedly formed by insertion of Ni0, Pd0, and FeI into the P−P bonds of a triphosphenium zwitterion, giving rise to structurally confirmed μ2‐bound monometallic or μ‐η1:η1‐bimetallic species. [ABSTRACT FROM AUTHOR]

Craftily crowned: The treatment of crown ether GeII dications with water or ammonia produces the stable complexes [([15]crown‐5)Ge⋅OH2][OTf]2 (see picture; Ge orange, O red, F green, S yellow, H blue) and [([15]crown‐5)Ge⋅NH3][OTf]2. The OH and NH hydrogen atoms are rendered more acidic in these compounds. [ABSTRACT FROM AUTHOR]

Review: notable aspects of the chemistry of polyether complexes of group 13 and 14 elements; 191 refs. [ABSTRACT FROM AUTHOR]