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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]

A series of germanium(II) and tin(II) bromide polyether complexes have been synthesized. Specifically, [GeBr([15]crown-5)] [Ge[Br.sub.3]], [GeBr([18]crown-6)][Ge[Br.sub.3]], [GeBr(triglyme)][Ge[Br.sub.3]], [GeBr(tetraglyme)][Ge[Br.sub.3]], [SnBr([18]crown-6)][Sn[Br.sub.3]], [Sn[([15]crown-5).sub.2]][Sn[[Br.sub.3]].sub.2], [SnBr(triglyme)][Sn[Br.sub.3]], and [SnBr(tetraglyme)][Sn[Br.sub.3]] have been fully characterized including by single crystal X-ray diffraction. The synthesis of [GeBr(dibenzo[24]crown-8)][Ge[Br.sub.3]] and [GeCl(dibenzo[24]crown-8)][Ge[Cl.sub.3]] are also reported, along with the crystal structure of the latter's water adduct, which features a water molecule adjacent to the Ge[Cl.sup.+] ion within the cavity of the crown ether. Key words: main group, polyether, crown ether, germanium and tin halides, group 14. Nous avons synthétisé une série de complexes de bromure de germanium(II) et d'étain(II) à base de polyéthers. En particulier, le [GeBit[15]couronne-5)][Ge[Br.sub.3]], le [GeBr([18]couronne-6)][Ge[Br.sub.3]], [GeBr(triglyme)][Ge[Br.sub.3]], le [GeBr(tétraglyme)][Ge[Br.sub.3]], le [SnBr([18]couronne-6)][Sn[Br.sub.3]], le [Sn([15]couronne-5)2][Sn[[Br.sub.3]].sub.2], le [SnBr(triglyme)][Sn[Br.sub.3]] et le [SnBr(tétraglyme)][Sn[Br.sub.3]] ont été soumis à une caractérisation complète, dont la diffraction des rayons X sur monocristal. Nous décrivons également la synthèse du [GeBr(dibenzo[24]couronne-8)][Ge[Br.sub.3]] et du [GeCl(dibenzo[24]couronne-8)][Ge[Cl.sub.3]], ainsi que la structure cristalline du dernier sous forme de produit d'addition avec l'eau, lequel présente une molécule d'eau adjacente à l'ion Ge[Cl.sup.+] à l'intérieur de la cavité de l'éther couronne. [Traduit par la Rédaction] Mots-clés: groupe principal, polyéther, éther couronne, halogénures de germanium et d'étain, groupe 14., Introduction The chemistry involving group 14 cations and polyether ligands has been an area of great interest over the last decade. (1) The complexation of lead(II) ions by macrocyclic polyethers [...]

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]

A series of complexes with the formulae [(BIMEt3)SnF4−x][OTf]x with x = 1–4 has been synthesized by successive fluoride abstraction from SnF4 with TMSOTf in the presence of the tetradentate nitrogen donor BIMEt3 (tris ((1-ethyl-benzoimidazol-2-yl)methyl)amine). Single crystal X-ray diffraction and heteronuclear NMR spectroscopic analysis provided insight into these new main group cations. Electrospray ionization mass spectrometric analysis on solutions containing the different salts allowed for successful detection of the cations [(BIMEt3)SnF]3+, [(BIMEt3)SnF2]2+ and [(BIMEt3)SnF3]+. [ABSTRACT FROM AUTHOR]

Two homologous series of pnictogen(III) dications, stabilized by 2,6-bis(benzimidazole-2-yl)pyridine ligands have been prepared. Both series contain PnIII-X moieties (Pn = P, As, Sb, Bi; X = Cl or Ph) and have been fully characterized using spectroscopic methods including X-ray crystallography. The Lewis acidity of these compounds has also been probed by computational methods; the results suggest that the dictations are strong Lewis acids, with the PnCl2+ compounds being more acidic than the PnPh2+ compounds, and with Lewis acidity increasing from P to Bi, in both series. The PhP2+-containing compound was also found to be a versatile PIII transfer reagent, leading to new synthetic routes for various PhP-containing compounds. The redox chemistry of all compounds has also been probed using cyclic voltammetry and chemical reductions. In some cases the resulting PnI moieties could be trapped using diazabutadienes., (© 2024 Wiley‐VCH GmbH.)

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., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Treatment of two equivalents of the triphosphenium zwitterion L with sources of Ni 0 and Pd 0 form the mononuclear η 2 -diphosphoniodiphosphene complexes 1 and 2. The reaction between L and [FeCp(CO) 2 ] 2 results in the binuclear μ-η 1 :η 1 -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., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Reported are general synthetic approaches for the syntheses of asymmetrically substituted phosphorus(I) cations by P + transfer from [dppeP] + (dppe = 1,2-bis(diphenylphosphino)ethane). The first method grants access to acyclic derivatives and is accomplished by the sequential substitution of dppe using first a sterically encumbered ligand which cannot form a stable homoleptic complex, followed by a second equivalent of a less sterically demanding ligand. The second method grants access to cyclic derivatives and utilizes asymmetric hybrid phosphine/N-heterocyclic carbene ligands. Interplay between the different ligand types and their stoichiometries relative to those of [dppeP] + also allows for the isolation of symmetrical derivatives with pendant phosphines.

A series of cationic complexes involving a pnictogen(iii) (Pn = P, As, Sb) centre and the tetradentate ligand tris((1-ethyl-benzoimidazol-2-yl)methyl)amine (BIMEt 3 ) have been synthesized and comprehensively characterized. Oxidation of [P(BIMEt 3 )] 3+ with XeF 2 provides access to [PF 2 (BIMEt 3 )] 3+ representing the first structurally characterized example of a phosphorus(v) centred trication.