Reactivity of tetrel functionalized heptapnictogen clusters towards heteroallenes

Abstract

Isocyanates and carbon dioxide capture between the tetrel-pnictogen bonds of functionalized [P7] cages is investigated by NMR and IR spectroscopy, signal crystal X-ray diffraction, and density functional theory.

Zintl Ions and Phases Promote the Catalytic Hydrophosphination of Alkynes, Alkenes, and Imines

“…As the unfunctionalized cluster A was able to promote hydrophosphination reactions, other pnictogen and tetrel Zintl ions and phases were also investigated in this transformation. Zintl ions [K­(DME) x ] 3 [P 7 ] ( B ) and [K­(DME) x ] 3 [As 7 ] ( C ) can both be synthesized by similar methods to A . , The DME content was similarly determined by elemental analysis and found to be 0.03 and 0.06/K cation for B ([K­(DME) 0.03 ] 3 [P 7 ]) and C ([K­(DME) 0.06 ] 3 [As 7 ]), respectively. Further, a range of Zintl phases, namely, K 3 P 7 ( D ), K 3 Sb 7 ( E ), K 5 Bi 4 ( F ), K 4 Ge 9 ( G ), and K 4 Sn 9 ( H ), were prepared following literature known methods.…”

“…Zintl ions and phases have been known for over a century but remained largely ignored. Their chemistry is now experiencing a renaissance, with developments as ligands in coordination chemistry, which have unlocked unique physical properties, in small molecule activations including reactivity akin to frustrated Lewis pair chemistry, , and as precursors to nanostructures and light-emitting diodes . One burgeoning area is the application of these ions and phases in organic catalysis.…”

Zintl Clusters as a Platform for Lewis Acid Catalysis

“…Previously, parallel reactivity between the [P 7 ] and the [As 7 ] clusters has been reported; , thus, we set out to make the [As 7 ] analogue of 1 . To this end, we first attempted to synthesize ({C 8 H 14 }BCH 2 CH 2 SiMe 2 ) 3 As 7 ( 7 ) from the salt metathesis reaction of [K(DME) x ] 3 [As 7 ] and the previously reported ClSiMe 2 CH 2 CH 2 B{C 8 H 14 } ( 8 ) chlorosilane; however, no conversion was detected by 29 Si{ 1 H} NMR spectroscopy even after 1 week in toluene.…”

“…Anionic clusters of main group elements, called Zintl clusters, have been known for over a century, but investigations into their subsequent chemistry has remained largely ignored. Recently, their chemistry is experiencing a resurgence with these clusters being employed as ligands on d- and f-block metals allowing access to unique physical properties, as components for small molecule capture and “frustrated Lewis pair” chemistry, and as precursors to controlled nanostructures and light emitting diodes. − One growing area of interest is the application of these clusters in catalytic science. These clusters are of interest because they can be understood as potential molecular prototypes for heterogeneous materials. − For instance, red phosphorus structurally resembles clusters of phosphorus coupled and cross-linked together .…”

Reactivity of Tetrel-Functionalized Heptaphosphane Clusters toward Azides

“…19 Next, following literature protocols, the tetrelfunctionalized clusters (Me 3 Si) 3 P 7 (1) and (Me 3 Ge) 3 P 7 (2) shown in Scheme 1 were prepared via salt elimination of [Na(DME) x ] 3 [P 7 ] with the corresponding tetrel chloride, Me 3 ECl (E = Si, Ge). 13,14 These tetrel-functionalized clusters were then allowed to react with organoazides, including benzyl azide (BnN 3 ), phenyl azide (PhN 3 ), and 4-bromophenyl azide (4-BrPhN 3 ). When a tetrahydrofuran (THF) solution of 1 was allowed to react with a solution of 3 equiv of BnN 3 , an immediate color change from pale yellow to deeper yellow was observed along with gas evolution, which was presumed to be N 2 (Scheme 1).…”