Treatment of Silylene–Phosphinidene with Chalcogens Resulted Exclusively in the Formation of Silicon‐Bonded Chalcogens

Abstract

Chalcogen‐bonded silicon phosphinidenes LSi(E)−P−MecAAC (E=S (1); Se (2); Te (3); L=PhC(NtBu)2; MecAAC=C(CH2)(CMe2)2N‐2,6‐iPr2C6H3)) were synthesized from the reactions of silylene–phosphinidene LSi−P−MecAAC (A) with elemental chalcogens. All the compounds reported herein have been characterized by multinuclear NMR, elemental analyses, LIFDI‐MS, and single‐crystal X‐ray diffraction techniques. Furthermore, the regeneration of silylene–phosphinidene (A) was achieved from the reactions of 2–3 with L′Al (L′=HC{(CMe)(2,6‐iPr2C6H3N)}2). Theoretical studies on chalcogen‐bonded silicon phosphinidenes indicate that the Si−E (E=S, Se, Te) bond can be best represented as charge‐separated electron‐sharing σ‐bonding interaction between [LSi−P−MecAAC]+ and E−. The partial double‐bond character of Si−E is attributed to significant hyperconjugative donation from the lone pair on E− to the Si−N and Si−P σ*‐molecular orbitals.

Bonding Relationship between Silicon and Germanium with Group 13 and Heavier Elements of Groups 14–16

“…The silagermenylidene (87) has the potential to undergo [2 + 2] cycloaddition reaction with one equiv. of phenylacetylene to afford base-stabilized cyclic germylene (88) as yellow crystals (Scheme 31b).…”

“…In 2019, Stalke, Parameswaran and Roesky et al reported the first silicon-bonded chalcogen phosphinidene compounds. [88] First, silylene-phosphinidene (125) was prepared Scheme 44. Synthesis of arsagermene 121.…”

“…In 2019, Stalke, Parameswaran and Roesky et al . reported the first silicon‐bonded chalcogen phosphinidene compounds [88] . First, silylene‐phosphinidene ( 125 ) was prepared via a two‐step process: starting from a heteroleptic chloro silylene (LSiCl) and a chlorophosphinidene [89] .…”

Synthesis and Coordination Behavior of a New Hybrid Bidentate Ligand with Phosphine and Silylene Donors

“…In the subsequent studies, we found that the reaction of silylene‐phosphinidene with chalcogens resulted in the selective formation of silicon bonded chalcogen phosphinidenes ( F ) [22] . Silylenes were found to be strong σ‐donor ligands in comparison with phosphinidenes.…”

The Aluminyl Anion: A New Generation of Aluminium Nucleophile

“…The chemistry of 2 , in particular, is undergoing a recent renaissance, being a key reagent in a number of recent publications [12] . These recent reports include the activation of small molecules (CO, C 2 H 4 ), [12c,j] reduction chemistry (including that of benzene), [12b,e,i,k,m] cycloadditions [12a,d,g] and various bond activations including C−H and C−F [12c,f,h,l,n] . The vast majority of the reactions of 1 and 2 are best described as oxidative additions, although some evidence of nucleophilic behaviour has been reported (especially with electropositive metals/Lewis acids) and this has been exploited in the formation of Al‐metal donor/acceptor bonds [11] .…”