New Vistas in Chemistry and Applications of Primary Phosphines

Abstract

Primary phosphines (R-PH 2 ) are an important class of compounds in organophosphorus chemistry. Although discovered over a century ago, their chemistry and applications have gained prominence in recent years. This review discusses recent developments on synthesis, molecular structure, properties, and applications of primary phosphines. In particular, discussions on synthesis and properties emphasize recent results from our laboratory on the chemical architecture of amide, thioether, and carboxylate functionalized primary bisphosphines. The utility of bromo-and aminopropyl phosphines (X(CH 2 ) 3 PH 2 ; X=Br or NH 2 ) as building blocks to produce 'designer' primary phosphines that display exceptional oxidative stability is described. The review also discusses the utility of carboxylate functionalized primary phosphines for incorporation on to peptides and their potential applications in catalysis and biomedicine.

Phosphines and Related Tervalent Phosphorus Systems

“…It was established that such through-bond interactions result in a lowering of the optical HOMO-LUMO gap of the molecule, and that oxidation at phosphorus leads to low optical band gap electroactive materials. 803 The reactions of pentafluorophenylphosphonite and -phosphinite esters with activated alkynes, followed by hydrolysis, yield benzophosphole oxides, e.g., (285). 804 Interest has continued in studies of the thermal isomerisation of 1H-phospholes to the 2H-isomers, and the Diels-Alder and related cycloaddition reactions of the latter.…”

A pyrazolylamine‐phosphonate monoester chelator for the fac‐[M(CO)3]+ core (M = Re, 99mTc): synthesis, coordination properties and biological assessment

“…Similar to what has been previously described by Katti et al for this type of compounds, 4 presents a high degree of oxidative stability upon contact with atmospheric oxygen and water, and lack of reactivity toward solvents and different type of chemical functionalities. [7][8][9][10] The formylation of the P-H bonds, carried out in degassed ethanol with 37% aqueous formaldehyde gave, instead of the hydroxymethyl phosphine groups, the rare heterocyclic phosphazolidine compound 5 (yield: 92%). This intramolecular cyclization is not surprising since it is known that the condensation of primary phosphines with formaldehyde in the presence of secondary amines leads, in a Mannich-type reaction, to tertiary phosphines containing dialkylaminoethyl groups or to phosphazolidine derivatives.…”

“…Regarding phosphorus-containing ligands for biomedical applications, Katti et al have developed tri-and tetradentate chelators combining nitrogen or sulfur as donor atoms, and highly stable tertiary phosphines, namely hydroxymethyl phosphines, which allowed the labeling of tumor-seeking peptides with 99m Tc for potential use in nuclear medicine. [7][8][9][10] Most recently, a new BFCA containing a picolylamine-methylphosphonic acid ester group for the labeling of hydroxyl-containing biomolecules with the fac-½ 99m TcðCOÞ 3 þ core has been developed. 11 Aiming to develop new site-specific radiopharmaceuticals based on the organometallic approach, we have introduced in the past few years a new family of model ligands for the stabilization of the fac-½MðCOÞ 3 þ moiety (R ¼ 99m Tc, Re), which contains a common pyrazolyl-amine chelating unit (Figure 1), and an aromatic (L1) or aliphatic (L2) amine, or a carboxylic acid group (L3).…”

Preparation, Structure and Gold(I) Complexation of p-Xylylene-1,4-diphosphines

“…1,4-dimethyl-2,5-di(phosphinyl)benzene (1). It was hoped that owing to the reduced mobility of the -PH 2 groups this homologue should crystallize more readily than the parent compound and allow the determination of its crystal structure.…”

“…Primary phosphines RPH 2 are attracting current interest [1] owing to their synthetic potential a) for the preparation of new types of functional or chiral ligands [2], b) as substrates for hydrophosphination reactions [3] and c) for the construction of multidimensional frameworks [4]. Regarding the latter aspect, polyfunctional primary arylphosphines with a rigid skeleton are particularly useful for the design of chainlike polymers or sheet-like layer structures with a variety of connectivity motifs which depend on the substitution pattern of the parent aromatic hydrocarbon.…”