67950-05-4

Upstream product

• 2633-66-1 2-mesitylmagnesium bromide 
• 5806-59-7 mesityllithium 
• 576-83-0 2,4,6-trimethylphenyl bromide 

Downstream Products

• 23897-16-7 Bis(2,4,6-trimethylphenyl)phosphine oxide 
• 1732-66-7 dimesityl phosphine 
• 590418-90-9 2-{[bis-(2,4,6-trimethyl-phenyl)-phosphanyl]-methyl}-4,6-di-tert-butyl-pyridine 
• 873112-33-5 C₃₃H₄₀N₃P 
• 600709-31-7 3-[bis-(2,4,6-trimethyl-phenyl)-phosphinothioyl]-2-tert-butoxycarbonylamino-propionic acid methyl ester 
• 600709-40-8 3-[bis-(2,4,6-trimethyl-phenyl)-phosphinothioyl]-2-tert-butoxycarbonylamino-propionic acid 
• 1003010-54-5 dimesitylvinylphosphine 
• 235422-44-3 Mes₂PCH₂SnPh₃ 
• 1086529-40-9 dimesityl(prop-1-ynyl)phosphane 
• 61123-81-7 (dimesitylphosphanyl)phenylacetylene 
• 1200436-04-9 bis(dimesitylphosphino)acetonitrile 
• 1144507-18-5 dimesityl(trans-2-(trimethylsilyl)vinyl)phosphane 
• 1144507-17-4 dimesityl(1-phenylvinyl)phosphane 
• 1144507-14-1 (1-methylethenyl)dimesitylphosphane 

Relevant academic research and scientific papers

Reshaping Membrane Polymorphism of Polymer Vesicles through Dynamic Gas Exchange

The quest for a universal method to shape the vesicular morphology in dynamic and diversified manners is a challenging topic of cell mimicry. Here we present a simple gas exchange strategy that can direct the deformation movements of polymer vesicles. Suc

Efficient Intramolecular Charge-Transfer Fluorophores Based on Substituted Triphenylphosphine Donors

Triphenylphosphine (TPP)-based luminescent compounds are rarely investigated because of the low photoluminescence quantum yield (PLQY). Here, we demonstrate that introducing steric hindrance groups to the TPP moiety and separating the orbitals involved in the transition can drastically suppress the non-radiative decay induced by structural distortion of TPP in the excited state. High PLQY up to 0.89 as well as thermally activated delayed fluorescence are observed from the intramolecular charge-transfer (ICT) molecules with substituted TPP donors (sTPPs) in doped films. The red organic light-emitting diodes employing these emitters achieve comparable external quantum efficiencies to the control device containing a classical phosphorescent dye, revealing the great potential of the ICT emitters based on electrochemically stable sTPPs.

Phosphine-catalysed reductive coupling of dihalophosphanes

Classically tetraaryl diphosphanes have been synthesized through Wurtz-type reductive coupling of halophosphanes R2PX or more recently, through the dehydrocoupling of phosphines R2PH. Catalytic variants of the dehydrocoupling reactio

Palladium-Based Hydroamination Catalysts Employing Sterically Demanding 3-Iminophosphines: Branched Kinetic Products by Prevention of Allylamine Isomerization

A new allylpalladium triflate catalyst with a dimesitylphosphine moiety was synthesized, isolated, and characterized. The greatly increased steric bulk on the phosphine of this palladium catalyst inhibited product isomerization, which is often observed after hydroamination of terminal allenes with secondary amines. The considerably reduced rate of isomerization facilitated the isolation of many previously unknown branched allylamines, products that were inaccessible when using other, more active 3-iminophosphine palladium catalysts.

Frustrated Lewis Pair Polymers as Responsive Self-Healing Gels

Steric bulk prevents the formation of strong bonds between Lewis acids and bases in frustrated Lewis pairs (FLPs), where latent reactivity makes these reagents transformative in small molecule activations and metal-free catalysis. However, their use as a platform for developing materials chemistry is unexplored. Here we report a fully macromolecular FLP, built from linear copolymers that containing either a sterically encumbered Lewis base or Lewis acid as a pendant functional group. The target functional copolymers were prepared by a controlled radical copolymerization of styrene with designer boron or phosphorus containing monomers. Mixtures of the B- and P-functionalized polystyrenes do not react, with the steric bulk of the functional monomers preventing the favorable Lewis acid base interaction. Addition of a small molecule (diethyl azodicarboxylate) promotes rapid network formation, cross-linking the reactive polymer chains. The resulting gel is dynamic, can self-heal, is heat responsive, and can be reshaped by postgelation processing.

Cyclometalated iridium complexes of bis(aryl) phosphine ligands: Catalytic C-H/C-D exchanges and C-C coupling reactions

This work details the synthesis and structural identification of a series of complexes of the (η5-C5Me5)Ir(III) unit coordinated to cyclometalated bis(aryl)phosphine ligands, PR′(Ar) 2, for R′ = Me and Ar = 2,4,6-Me3C6H 2, 1b; 2,6-Me2-4-OMe-C6H2, 1c; 2,6-Me2-4-F-C6H2, 1d; R′ = Et, Ar = 2,6-Me2C6H3, 1e. Both chloride-and hydride-containing compounds, 2b-2e and 3b-3e, respectively, are described. Reactions of chlorides 2 with NaBArF (BArF = B(3,5-C 6H3(CF3)2)4) in the presence of CO form cationic carbonyl complexes, 4+, with ν(CO) values in the narrow interval 2030-2040 cm-1, indicating similar π-basicity of the Ir(III) center of these complexes. In the absence of CO, NaBArF forces κ4-P,C,C′,C″ coordination of the metalated arm (studied for the selected complexes 5b, 5d, and 5e), a binding mode so far encountered only when the phosphine contains two benzylic groups. A base-catalyzed intramolecular, dehydrogenative, C-C coupling reaction converts the κ4 species 5d and 5e into the corresponding hydrido phosphepine complexes 6d and 6e. Using CD3OD as the source of deuterium, the chlorides 2 undergo deuteration of their 11 benzylic positions whereas hydrides 3 experience only D incorporation into the Ir-H and Ir-CH 2 sites. Mechanistic schemes that explain this diversity have come to light thanks to experimental and theoretical DFT studies that are also reported.

Development of efficient and reusable diarylphosphinopolystyrene-supported palladium catalysts for C-C bond forming cross-coupling reactions

Short and versatile syntheses of reusable diarylphosphinopolystyrene- supported palladium catalysts 3a-j are described. The bis(o-tolyl)phosphino catalyst 3b is particularly efficient for the Suzuki and Sonogashira cross-couplings, whereas the bis(m-tolyl)phosphino catalyst 3c is the most active catalyst for Heck reactions. The couplings are performed under non-anhydrous reaction conditions and require only low amounts of supported palladium (0.5 mequivs. for Suzuki-Miyaura, 1.0 mequiv. for Sonogashira and 0.5 mequivs. for Heck reactions could be sufficient). Catalysts 3a-j are recovered by filtration and can be reused more than four times with no loss of efficiency.

Syntheses, structures, and redox properties of 1,4- bis(dimesityiphosphino)-2,3,5,6-tetrafluorobenzene and the corresponding bis(phosphoryl) and bis(phosphonio) derivatives

Sterically hindered 1,4-bis(dimesitylphosphino)-2,3,5,6- tetrafluorobenzene (1) was synthesized by the aromatic nucleophilic substitution of lithium dimesitylphosphide with hexafluorobenzene. Two phosphorus atoms of I were oxidized and methylated to give the corresponding bis(phosphoryl)benzene 2 and bis(phosphonio)benzene 32+·2TfO-(TfO- = trifluoromethanesulfonyl), respectively. On the other hand, reaction of 1 with butyllithium and phenyllithium gave more crowded 2,5-dibutyl-1,4- bis(dimesitylphosphino)-3,6-difluorobenzene (4) and 1,4- bis(dimesitylphosphino)2,5-difluoro-3,6-diphenylbenzene (5), respectively. Structures of l, 2, 32+·2TfO-, 4, and 5 were confirmed by conventional spectroscopic methods; particularly 19F NMR spectroscopy reflected their crowded structures. Molecular structures of 1, 2, and 32+·2TfO-, were further investigated by X-ray crystallography, where unusually large bond angles around phosphorus atoms were observed. Electrochemical measurements were carried out to investigate redox properties of 1, 32+·2TFO-, 4, and 5. Although the cyclic voltammogram of diphosphine 1 showed irreversible oxidation waves above 0.8 V, in spite of substitution at all the ortho positions to the phosphorus atoms in 1, displacement of the two fluorine atoms of 1 by the butyl or the phenyl groups lowered the oxidation potential and improved the stability of the corresponding radical cations. Particularly, 5 clearly showed two-step oxidation waves. On the other hand, bis(phosphonium salt) 32+·2TfO- showed two steps of quasi-reversible redox waves, which suggested reduction to the cation radical and the neutral species, although their stability was limited.

PHOSPHORUS-PHOSPHORUS SINGLE OR DOUBLE BOND FORMATION FROM PCl(3-n)Rn (n=1 or 2) AND A BIS-IMIDAZOLIDINE REDUCING AGENT

1,3,1'.3'-Tetraethyl-bis(2,2'-imidazolidene), L2Et (I), is a mild homogeneous reducing agent which reduces P-Cl bonds phosphonous or phosphinous chlorides to give compounds with phosphorus-phosphorus bonds.High yields of diphosphines P2R4 are produced from the corresponding phosphinous chlorides (PClR2).Phenyl- and t-butyl-phosphonous dichlorides are reduced to cyclopolyphosphines (PR)n, which appear to be the kinetically controlled products. 2,4,6-Tri(t-butyl)phenylphosphonous dichloride (PArCl2) is reduced to either 1,2-dichloro-1,2,bis(2,4,6-tri-t-butylphenyl)diphosphine (PArCl)2 or trans-bisdiphosphene (P2Ar2) depending on the initial stoichiometry.

Rearrangements of the Methyltrimesitylphosphonium and Methylenebis(methyldimesitylphosphonium) Cation Skeletons on Treatment with Base

The treatment of methyltrimesitylphosphonium iodide (1) with sodium amide or butyllithium leads neither to the corresponding phosphorus ylide nor to the product of a Stevens rearrangement, but affords instead methylmesitylphosphane (4).The product, which is probably formed via a mesityl migration in an 2-methylenecyclohexadienylidenephosphorane intermediate (2b), is structurally characterized by detailed NMR analysis and through hydrochloride and methoiodide derivatives. - Analogous treatment of methylenebis(methyldimesitylphosphonium iodide) (10) with base leads to a pair of diastereomeric cyclic carbodiphosphoranes (12a, b), with elimination of mesitylene.The two carbodiphosphoranes are converted into the diastereomeric diphosphonium salts 13a, b with HCl.The ring closure leading to carbodiphosphorane formation is again interpreted in terms of an intramolecular process involving an 2-methylenecyclohexadienylidene intermediate.Deprotonation of the methylenebis(methyldi-o-tolylphosphonium) cation yields the corresponding carbodiphosphorane 18 without changes in the skeleton.