Nitrogen–Phosphorus(III)–Chalcogen Macrocycles for the Synthesis of Polynuclear Silver(I) Sandwich Complexes

The synthesis of inorganic N–P­(III)-Ch-based macrocycles [−PhP–NMe–PPh–Ch−]₂ (<b>8</b>_<b>Ch</b>; Ch = S, Se) is presented by incorporating two nitrogen, two chalcogen, and four phosphorus atoms. The macrocycles are conveniently obtained via the cyclocondensation reaction of Na₂Ch (Ch = S, Se) with the acyclic dichlorodiphosphazane ClPhP–NMe–PClPh (<b>9</b>). Treatment with elemental sulfur (S₈) or gray selenium (Se_gray) results in an oxidative ring contraction to give 1,3,2,4-thiazadiphosphetidine 2,4-disulfide (<b>10</b>_<b>S</b>) and 1,3,2,4-selenazadiphosphetidine 2,4-diselenide (<b>10</b>_<b>Se</b>), respectively. Macrocycles <b>8</b>_<b>Ch</b> are excellent multidentate ligands for transition metal complexation, as demonstrated by the isolation of mono-, di- tri-, and tetranuclear silver sandwich complexes. The polynuclear silver complexes are comprehensively characterized, including detailed NMR and X-ray analysis

Nitrogen–Phosphorus(III)–Chalcogen Macrocycles for the Synthesis of Polynuclear Silver(I) Sandwich Complexes

The synthesis of inorganic N–P­(III)-Ch-based macrocycles [−PhP–NMe–PPh–Ch−]₂ (<b>8</b>_<b>Ch</b>; Ch = S, Se) is presented by incorporating two nitrogen, two chalcogen, and four phosphorus atoms. The macrocycles are conveniently obtained via the cyclocondensation reaction of Na₂Ch (Ch = S, Se) with the acyclic dichlorodiphosphazane ClPhP–NMe–PClPh (<b>9</b>). Treatment with elemental sulfur (S₈) or gray selenium (Se_gray) results in an oxidative ring contraction to give 1,3,2,4-thiazadiphosphetidine 2,4-disulfide (<b>10</b>_<b>S</b>) and 1,3,2,4-selenazadiphosphetidine 2,4-diselenide (<b>10</b>_<b>Se</b>), respectively. Macrocycles <b>8</b>_<b>Ch</b> are excellent multidentate ligands for transition metal complexation, as demonstrated by the isolation of mono-, di- tri-, and tetranuclear silver sandwich complexes. The polynuclear silver complexes are comprehensively characterized, including detailed NMR and X-ray analysis

Condensation Reactions of Chlorophosphanes with Chalcogenides

A high-yielding and facile synthesis for diphosphane monochalcogenides (1(Ch)((R))) and their constitutional isomers, diphosphanylchalcoganes (2(Ch)((R))), was developed, featuring a condensation reaction between chlorophosphanes (R2PCl) and sodium chalcogenides (Na(2)Ch, Ch = S, Se, (Te)). The optimized protocol selectively yields either 1(Ch)((R)) (R-2(Ch)PPR2) or 2(Ch)((R)) (Ch(PR2)(2)) depending upon the steric demand of the substituents R Reaction pathways consistent with the distinct reaction outcomes are proposed. The application of I-h((R)) and 2(Ch)((R)) as an interesting dass of ligands is exemplarily demonstrated by the preparation of selected transition metal complexes

Novel synthetic pathway for the production of phosgene

Chloride ions are efficient catalysts for the synthesis of phosgene from carbon monoxide and elemental chlorine at room temperature and atmospheric pressure. Control experiments rule out a radical mechanism and highlight the role of triethylmethylammonium trichloride, [NEt3Me][Cl3], as active species. In the catalytic reaction, commercially available [NEt3Me]Cl reacts with Cl2 to form [NEt3Me][Cl3], enabling the insertion of CO into an activated Cl─Cl bond with a calculated energy barrier of 56.9 to 77.6 kJ mol−1. As [NEt3Me]Cl is also a useful chlorine storage medium, it could serve as a catalyst for phosgene production and as chlorine storage in a combined industrial process

Reductive Ring Opening of a Cyclo-Tri(phosphonio)methanide Dication to a Phosphanylcarbodiphosphorane: <i>In Situ</i> UV-Vis Spectroelectrochemistry and Gold Coordination

The formal two-electron reduction of the cyclo-tri­(phosphonio)­methanide dication <b>1</b>²⁺ results in a ring-opening reaction via C–P bond cleavage to yield the unique phosphanyl-functionalized carbodiphosphorane <b>2</b>. <i>In situ</i> spectroelectrochemical investigations of the reduction of dication <b>1</b>²⁺ and the oxidation of <b>2</b> give insights into the mechanism of this unusual and reversible bond cleavage reaction. Compound <b>2</b> features in total three lone pairs of electrons, facilitating the preparation of mono-, di-, and trigold complexes

Condensation Reactions of Chlorophosphanes with Chalcogenides

A high-yielding and facile synthesis for diphosphane monochalcogenides (<b>1</b>_Ch^(R)) and their constitutional isomers, diphosphanylchalcoganes (<b>2</b>_Ch^(R)), was developed, featuring a condensation reaction between chlorophosphanes (R₂PCl) and sodium chalcogenides (Na₂Ch, Ch = S, Se, (Te)). The optimized protocol selectively yields either <b>1</b>_Ch^(R) (R₂(Ch)­PPR₂) or <b>2</b>_Ch^(R) (Ch­(PR₂)₂) depending upon the steric demand of the substituents R. Reaction pathways consistent with the distinct reaction outcomes are proposed. The application of <b>1</b>_Ch^(R) and <b>2</b>_Ch^(R) as an interesting class of ligands is exemplarily demonstrated by the preparation of selected transition metal complexes