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Usage

Uses

Used in Organometallic Chemistry:
1,3-Bis(diphenylphosphinomethyl)benzene is used as a reactant for cyclometalation of pincer ligands, which are crucial in the formation of stable metal complexes with potential applications in catalysis and other areas.
Used in Carbon Dioxide Insertion:
1,3-Bis(diphenylphosphinomethyl)benzene serves as a reactant in the insertion of carbon dioxide into (PCP)PDII-Me Bonds, a process that can lead to the development of new materials and compounds with potential applications in various industries.
Used in Iridium Complex Synthesis:
1,3-Bis(diphenylphosphinomethyl)benzene is used as a reactant in the synthesis of iridium complexes containing bidentate phosphine ligands. These complexes are of interest in the field of homogeneous catalysis and can be employed in various chemical transformations.
Used in Transcyclometalation Processes:
1,3-Bis(diphenylphosphinomethyl)benzene is utilized in transcyclometalation processes, which involve the transfer of a metal-carbon bond from one ligand to another. This process is important in the synthesis of various organometallic complexes with potential applications in catalysis and materials science.
Used in Vinylidene and Carbyne Complex Synthesis:
1,3-Bis(diphenylphosphinomethyl)benzene is used as a reactant in the synthesis of vinylidene and carbyne complexes. These complexes are of interest in the study of organometallic chemistry and can be used as catalysts or precursors in various chemical reactions.

Upstream product

• 4376-01-6 sodium diphenylphosphide 
• 626-15-3 1,3-bis-(bromomethyl)benzene 
• 65567-06-8 lithium diphenylphosphide 
• 626-16-4 3-(chloromethyl)benzyl chloride 
• 829-85-6 diphenylphosphane 
• 1079-66-9 chloro-diphenylphosphine 
• 73207-71-3 (1,3-phenylenebis(methylene))bis(diphenylphosphine oxide) 
• 15475-27-1 potassium diphenylphosphine 

Downstream Products

• 73207-71-3 (1,3-phenylenebis(methylene))bis(diphenylphosphine oxide) 
• 89673-24-5 [C₆H₃(CH₂P(C₆H₅)2)2PtBr] 
• 321126-12-9 [PtCl(η1-C-C6H3(CH2NMe2)2-2,6)(C6H4(CH2PPh2)2-1,3)]2 
• 159983-97-8 Ag₂Cl₂(1,3-bis[(diphenylphosphino)methyl]benzene)2 
• 197019-18-4 1,3-(Ph₂PCH₂)2C₆H₃-2-Ru(1,3-(Ph₂PCH₂)2C₆H₄)CF₃SO₃ 
• 172295-98-6 [Rh(C₆H₃(CH₂P(C₆H₅)2)2)(P(C₆H₅)3)(H)(Cl)] 
• 271598-15-3 [RhCl(COD)]2(μ2-(1,3-(PPh2CH2)2C6H4)) 
• 376354-48-2 [((CH₂P(C₆H₅)2)2C₆H₃)Pt(C₃F₇)] 
• 631898-31-2 (2,6-bis[(diphenylphosphino)methyl]phenyl)(trifluoroacetato)palladium(II) 
• 184714-11-2 (2,6-bis[(diphenylphosphino)methyl]phenyl)chloro(triphenylphosphine)ruthenium(II) 

Relevant academic research and scientific papers

One-Pot Synthesis of 1,3-Bis(phosphinomethyl)arene PCP/PNP Pincer Ligands and Their Nickel Complexes

A one-pot synthesis of arene-based PCP/PNP ligands has been developed. The reaction of 1,3-bis(bromomethyl)benzene or 2,6-bis(bromomethyl)pyridine with various chlorophosphines in acetonitrile afforded bis-phosphonium salts. These salts can then be reduced by magnesium powder to yield PCP or PNP ligands. In comparison to traditional synthetic methods for making PCP/PNP ligands involving the use of secondary phosphines, this new alternative method allows for the use of chlorophosphines, which are cheaper, safer to handle, and have a broader range of commercially available derivatives. This is especially true for the chlorophosphines with less bulky alkyl groups. Moreover, the one-pot procedure can be extended to allow for the direct synthesis of PCP/PNP nickel complexes. By using nickel powder as the reductant, the resulting nickel halide was found to directly undergo metalation with the PCP or PNP ligand to generate nickel complexes in high yields.

Carboxylation of pincer PCP platinum methoxide complexes under formation of metalla carbonates

The ligand 2,6-bis[(diphenylphosphino)methyl]benzene ((PCP)H) was prepared and characterised in an improved manner. With platinum it forms the complex (PCP)PtOTf which reacts with sodium methoxide to give (PCP)PtOMe as the major product together with a sm

A recyclable perfluoroalkylated PCP pincer palladium complex

A new fluorous PCP pincer ligand has been coordinated to Ni(ii), Pd(ii) and Pt(ii). The air stable palladium complex, which promotes Heck reactions between methyl acrylate and either aryl bromides or iodides, can be recovered intact by fluorous solid-phase extraction and was reused four times in the Heck reaction between methyl acrylate and 4-bromoacetophenone without loss in catalytic activity. The Royal Society of Chemistry 2011.

O-Semiquinonic PCP-pincer nickel complexes with alkyl substituents: Versatile coordination sphere dynamics

o-Semiquinonic nickel pincer complexes (R2PCP)Ni(SQ) show a versatile coordination sphere dynamics via swing or fan oscillations depending on the steric properties of the phosphorus substituents. The Royal Society of Chemistry.

A catalytic and mechanistic investigation of a PCP pincer palladium complex in the Stille reaction

In an improved procedure, the complex {2,6-bis[(diphenylphosphino)methyl] benzene}chloropalladium(II) (1) was synthesised as its THF adduct and the structure was determined by X-ray crystallography. The catalytic properties of the derivative {2,6-bis[(diphenylphosphino)methyl]benzene}(trmuoroacetato) palladium(II) (2) was investigated in the Stille reaction. Complex 2 proves to be an excellent catalyst for the C-C cross-coupling between trimethyl phenyl stannane and aryl bromides using a very low catalyst loading (0.1-0.0001%), giving high turnover numbers (TONs) up to 6.9 × 105. A kinetic investigation of the catalytic reaction suggests a heterogeneous colloidal palladium catalyst formed from the PCP Pd(II) pre-catalyst. The Royal Society of Chemistry 2005.

The methylene-transfer reaction: Synthetic and mechanistic aspects of a unique C-C coupling and C-C bond activation sequence

Oxidative addition of aryl iodides ArI (Ar = (a) C6H5, (b) C6H4CF3, (c) C6H3(CF3)2, (d) C6H4CH3, (e) C6H4OCH3), to the PCP-type complex Rh(PPh3)[CH2C6H(CH3)2(CH2PPh2)2] (1), yields the complexes Rh(Ar)[CH2C6H(CH3)2(CH2PPh2)2](I) (2a-e). Compounds 2a-e undergo intramolecular methylene transfer from the bis-chelating ligand to the incoming aryl under mild conditions (room temperature) giving Rh(CH2-Ar)[C6H(CH3)2(CH2PPh2)2](I) (3a-e). The methylene transfer, which is a unique sequence of sp2-sp3 C-C bond reductive elimination and sp2-sp3 C-C bond activation, was investigated kinetically (reaction 2a → 3a), yielding the activation parameters ΔH(+) = 17 ± 3 kcal/mol, ΔS(+) = -23 ± 4 eu. The rate-determining step of this reaction is the C-C reductive elimination rather than the C-C activation step. X-ray structural analysis of 2a and 3b demonstrates that the Rh atom is located in the center of a square pyramid with the aryl (2a) and the benzyl (3b) trans to the vacant coordination site. Reaction of the complex Rh(CH2C6H4CF3)[C6H3(CH2PPh2)2](Br) (7c) with carbon nucleophiles (MeLi, PhLi, BzMgCl) leads to a competitive sp2-sp3 and sp3-sp3 C-C coupling, resulting in migration of a methylene or benzylidene into the bis-chelating ring and formation of the corresponding organic products, sp2-sp3 C-C coupling was shown to be kinetically preferred over the sp3-sp3 one, and the more electron-rich the benzyl ligand, the better the migratory aptitude observed. X-ray structural analysis of two benzyl migration products, complexes Rh(PPh3)[CH(C6H4CF3)C6H3(CH2PPh2)2] (11) and Rh(PPh3)[CH(C6H5)C6H(CH3)2(CH2PPh2)2] (16), demonstrates that the rhodium atom is located in the center of a square planar arrangement where the PPh3 ligand occupies the position trans to the methyne carbon of the benzylidene bridge. The methylene and benzylidene migration reaction is an important transformation for the regeneration of the methylene-donating moiety in the methylene-transfer process.

Using polarization effects to alter chemical reactivity: A simple host which enhances amine nucleophilicity

(Matrix Presented) The rational design of a bis(phosphine oxide) host which is capable of binding a benzylic amine is presented. The ability of this host to increase the rate of addition of 4-fluorobenzylamine to N-phenylmaleimide is rationalized in terms of the enhancement of the nucleophilicity of the benzylic amine.

THE FACILE CYCLOMETALLATION REACTION OF 1,3-BISBENZENE

It is shown that 1,3-bis(diphenylphosphinomethyl)benzene (PCHP) readily undergoes a cyclometallation reaction with nickel(II), palladium(II), and platinum(II) species giving products of the type M=Ni, Pd, and Pt; X=halide and PCP=2,6-bis(diphen