Carbene-Stabilized Parent Phosphinidene

Abstract

The lithiated N-heterocyclic carbene−phosphinidene adduct L′:P−H (3; L′: = :C{[N(2,6-Pri 2C6H3)]2CHCLi(THF)3}) unexpectedly resulted from the reaction of lithium metal with the carbene-stabilized diphosphorus species L:P−P:L (2; L: = :C{N(2,6-Pri 2C6H3)CH}2). Compound 2 was previously prepared by the potassium graphite reduction of L:PCl3 (1).

Advanced NMR Methods and DFT Calculations on the Regioselective Deprotonation and Functionalization of 1,1′‐Methylenebis(3‐methylimidazole‐2‐thione)

“…This intermediates attracted the attention of the researchers, and subsequent work focused on the isolation and characterization of this type of NHC, which was crowned by the successful synthesis of the first crystalline carbene 1,3‐di(adamantyl)imidazol‐2‐ylidene . These fundamental findings reopened doors towards multifaceted (N‐heterocyclic) carbene chemistry and set off an avalanche of preparations of different types of carbenes and their diverse applications in inorganic chemistry, such as the metal‐free activation and stabilization of reactive main‐group elements and compounds and the syntheses of anionic N‐heterocyclic dicarbenes and their reactivity towards highly reactive main‐group molecules . Furthermore, the so‐called “abnormal” bonding mode in carbene complexes and the specific generation and isolation of abnormal carbenes (aNHCs, or mesoionic NHCs) also attracted the attention of synthetic chemists.…”

Coordination chemistry of ditopic carbanionic N-heterocyclic carbenes

“…Having synthesized an NHC-stabilized diphosphorus fragment by the reduction of the NHC-PCl 3 adduct with KC 8 , Robinson and co-workers were able to reduce this species further using lithium metal in THF to afford the anionic carbene-stabilized parent phosphinidene 31 [89], where the "normal" carbene position is bound to the phosphinidene moiety and the carbanionic backbone coordinated to a solvated lithium cation (Fig. 17).…”

“…Chemical reduction of a NHC-stabilized P2 moiety to afford a phosphinidine bonded to a ditopic carbanionic carbene[89].…”

Coordination‐Like Chemistry of Phosphinidenes by Phosphanes

“…Adducts of stable carbenes and phosphinidenes are also known. [76] These types of compounds will surely grow in significance as their exciting chemistry is further explored. [75] Most recently, an ex-ample of a carbene-stabilized "PH" has appeared.…”