Blocking Intramolecular Cycloadditions between C≡C Triple Bonds and Electrophilic Phosphinidene Complexes: Generation of Intermediates Able To React with Arenes

Abstract

Electrophilic terminal phosphinidene complexes [R1P-W­(CO)5] bearing 2-alkynylphenyl R1 substituents undergo a spontaneous cyclization to give intermediate five-membered species which are able to perform an electrophilic substitution reaction with toluene and mesitylene. An intramolecular version of this reaction is possible with appropriate R substituents on the CC triple bond.

Aspects of Phosphaallene Chemistry: Heat-Induced Formation of 1,2-Dihydrophosphetes by Intramolecular Nucleophilic Aromatic Substitution and Photochemical Generation of Tricyclic Phosphiranes

“…The structures may be compared to those of some P peri-bridged naphthalenes . The P atoms have a distorted tetrahedral environment with P–W bond lengths of about 2.50 Å which compare well to those of W­(CO) 5 complexes of secondary phosphines. ,,, …”

Sterically constrained tricyclic phosphine: redox behaviour, reductive and oxidative cleavage of P–C bonds, generation of a dilithium phosphaindole as a promising synthon in phosphine chemistry

“…The P1–W1 distance [252.9(1) pm] is in the typical range. 33 The P1–C1 distance [177.9(2) pm] is shorter than that one in 7 [179.8(3) pm], the other P–C distances approach the standard value and are between 182.3(2) and 185.2(2) pm. In contrast to the molecular structure of 7 , the phenyl group attached to P2 adopts an endo -position, and the SiMe 2 Ph groups change their orientation with all three phenyl groups in neighboring positions (compare Fig.…”

Phosphafluorenyl lithiums: direct synthesis from white phosphorus, structure and diversified synthons

“…Phospholides are the key intermediates to realize many transformations for the synthesis of organophosphorus compounds, which have played a very important role in chemical research and our daily life [1][2][3]. As the cyclic phospholides, phospholyl anions (Scheme 1-I) have received much attention because they can stabilize many metal complexes or act as the precursors for the synthesis of phospholes (Scheme 1-II) [4][5][6][7][8][9][10]. In contrast to the rich chemistry of phospholyl anions, phosphafluorenyl anions (Scheme 1-III) are only proposed as the critical intermediates for the synthesis of phosphafluorenes (dibenzophospholes) (Scheme 1-IV), which have a wide range of applications because they can serve as (1) suitable ligands in organometallic chemistry and organic synthesis methodology [11][12][13]; (2) organocatalysts in some classic organic reactions (e.g., Appel reaction, Staudinger reaction) [14,15]; and (3) organic optoelectronic materials [16][17][18][19].…”