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Relevant academic research and scientific papers

An examination of the effects of borate group proximity on phosphine donor power in anionic (phosphino)tetraphenylborate ligands

The ligand electron-donating abilities are compared among a series of monodentate, anionic (phosphino)tetraphenylborate phosphines [Ph4P][Ph2P-R-C6H4BPh3] (R = -C6H4-, -CH2-, -CH2CH2- or none), and their neutral counterparts Ph2PR (R = biphenyl, -CH2Ph, -CH2CH2Ph or Ph). Among the anionic ligands, the position of the tetraphenylborate group relative to the diphenylphosphino donor moiety was systematically varied in an effort to examine how its proximity impacts donor power. The donor power was determined by measuring the 31P-77Se coupling constant for the corresponding selenide of each phosphine ligand via 31P NMR spectroscopy. The anionic ligands yield lower 31P-77Se coupling constants than those measured for their respective neutral counterparts. Moreover, the 31P-77Se coupling constants among the anionic ligands increase when the tetraphenylborate group is positioned further from the phosphorus centre.

A bench-stable copper photocatalyst for the rapid hydrophosphination of activated and unactivated alkenes

Cu(acac)2 (1) is a highly active catalyst for the hydrophosphination of alkenes. Photocatalytic conditions are critical, and provide high conversions with unactivated substrates that have never before been reported with an air-stable catalyst or at ambient temperature. The commercial availability, ease of use, and broad substrate scope of compound 1 make hydrophosphination more available to synthetic chemists.

Hydrophosphination using [GeCl{N(SiMe3)2}3] as a pre-catalyst

Transformations catalyzed by germanium are scarce, with examples mainly limited to widely catalyzed processes such as polymerisation of lactide and hydroboration of carbonyls. Reported is the first example of hydrophosphination using a germanium pre-catalyst, yielding anti-Markovnikov products when diphenylphosphine is reacted with styrenes or internal alkynes at room temperature. This journal is

Catalyst-free hydrophosphination of alkenes in presence of 2-methyltetrahydrofuran: A green and easy access to a wide range of tertiary phosphines

A hydrophosphination reaction that is free of base, acid and catalyst, using only 2-methyltetrahydrofuran as additive has been performed. A new family of mono-, di-, tri- and tetra-phosphines compounds are obtained in good to excellent yields by adding di

Photocatalytic Hydrophosphination of Alkenes and Alkynes Using Diphenylphosphine and Triamidoamine-Supported Zirconium

Reactions of alkene or alkyne with diphenylphosphine and catalytic [κ5-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH2]Zr (1) are greatly enhanced under photolysis, providing viable catalytic hydrophosphination with a broad substrate scope. Whereas diphenylphosphine had been an inaccessible substrate under thermal conditions, complete conversion of alkene substrates to tertiary phosphine is achieved in as little as four hours at ambient temperature with 1 under ultraviolet irradiation. Previously inactive alkenes are now hydrophosphination substrates with diphenylphosphine to produce tertiary phosphine ligands possessing tunable steric and electronic properties.

Neutral and Cationic Zirconium Complexes Bearing Multidentate Aminophenolato Ligands for Hydrophosphination Reactions of Alkenes and Heterocumulenes

Zirconium complexes supported by multidentate aminophenolato ligands were synthesized and characterized. The catalytic activities of neutral zirconium complexes and their cationic derivatives in the hydrophosphination of alkenes as well as heterocumulenes have been investigated and compared. Neutral complex 1 bearing a multidentate amino mono(phenolato) ligand exhibited high activity in hydrophosphination of simple alkenes, and anti-Markovnikov products were obtained in 37-94% yields at room temperature. Cationic species generated in situ from complex 3 stabilized by a bis(phenolato) ligand were found to be more active for hydrophosphination of heterocumulenes, i.e., carbodiimides and isocyanates, and gave phosphaguanidines and phosphaureas in 67-93% yields. The Lewis acidity and coordination space of metal centers are modified through changes in the ligand structure, which is found to significantly influence catalytic activity. These complexes are among the most active group 4 metal-based catalysts for hydrophosphination reactions.

Three-carbon bridge joint guanidino- stable divalent europium complex and its preparation method and application

The invention discloses a divalent europium coordination compound with stable three-carbon bridging guanidyl, a preparation method therefor and an application thereof. Bridged guanidine lithium and europium trichloride react in a tetrahydrofuran solvent,

Tin-catalyzed hydrophosphination of alkenes

Simple tin derivatives, Cp?2SnCl2 (1) and Ph2SnCl2 (2), catalyze the hydrophosphination of alkene substrates with diphenylphosphine. Competitive dehydrocoupling to give Ph4P2 was observed, but this side reaction can be mitigated when the catalysis is conducted under an H2 atmosphere. Efforts to prepare stable tin bis(phosphido) compounds commonly resulted in decomposition to Ph4P2. Lewis acidic inorganic tin compounds do not show dehydrocoupling reactivity. It was found that the Lewis acid, B(C6F5)3, is able to engage in the hydrophosphination of alkenes, but it is poorly effective under the conditions tested.

N-Heterocyclic Carbene-Ytterbium Amide as a Recyclable Homogeneous Precatalyst for Hydrophosphination of Alkenes and Alkynes

The N-heterocyclic carbene-ytterbium(II) amides (NHC)2Yb[N(SiMe3)2]2 (1: NHC: 1,3,4,5-tetramethylimidazo-2-ylidene (IMe4); 2: NHC: 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IiPr)) and the NHC-stabilized rare-earth phosphide (IMe4)3Yb(PPh2)2 (3) have been synthesized and fully characterized. Complexes 1-3 are active precatalysts for the hydrophosphination of alkenes, alkynes, and dienes and exhibited much superior catalytic activity to that of the NHC-free amide (THF)2Yb[N(SiMe)2]2. Complex 1 is the most active precursor among the three complexes. In particular, complex 1 can be recycled and recovered from the reaction media after the catalytic reactions. Furthermore, it was found that complex 3 could catalyze the polymerization of styrene to yield atactic polystyrenes with low molecular weights. To the best of our knowledge, complex 1 represents the first rare-earth complex that can be recovered after catalytic reactions.

Synthesis and molecular structures of divalent bridged bis(guanidinate) europium complexes and their application in intermolecular hydrophosphination of alkenes and alkynes

The reaction of anhydrous EuCl3 with one equiv. of lithium salt of a three-carbon bridged bis(guanidinate) Li2L1 (L1 = [iPr(Me3Si)NC(NiPr)N(CH2)3NC(NiPr)N(SiMe3)iPr]) in THF afforded chloride EuIIIL1Cl(THF)2 (1). The reduction reaction of complex 1 with Na/K alloy in a molar ratio of 1?:?1.2 in THF gave a novel EuII complex supported by an unexpected new bridged bis(guanidinate) ligand L3, [EuIIL3]2 (L3 = [iPr(Me3Si)NC(NiPr)N(CH2)3N(SiMe3)C(NiPr)2]) (2), through the redistribution of one guanidinate in L1 during the reduction. Complex 2 was structurally characterized to be a binuclear complex in which two Eu metals are connected together by two L3 ligands that adopted a μ-η1:η2:η2 coordination mode for one L3 ligand and a μ-η2:η2:η2 mode for the other. Treatment of the in situ formed EuIIIL2Cl(THF)2 (L2 = 1,8-C10H6{NC(NiPr)(NHiPr)}2) by the reaction of EuCl3 with 0.5 equiv. of [Li2L22Li2] in THF with Na/K alloy yielded a novel EuII complex [EuIIL2(THF)]2 (3) in good yield. Complex 3 was characterized by an X-ray crystal structure analysis. Complex 3 features an unusual μ-η1:η2:η2 coordination mode of the bridged bis(guanidinate) ligand onto EuII. Complexes 2 and 3 are efficient pre-catalysts for the intermolecular hydrophosphination of alkenes and alkynes to give exclusively anti-Markovnikov products and mainly anti-addition products for the alkyne reactions. For these transformations, the best performances were observed with complex 2.