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Relevant academic research and scientific papers

Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts

Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compounds often demand either harsh reaction conditions, prefunctionalization of starting materials, highly sensitive organometallic reagents, or expensive transition-metal catalysts. Mild, practical methods thus remain elusive, despite being of great current interest. Herein, we describe a visible-light-driven method to form these products from secondary and primary phosphines. Using an inexpensive organic photocatalyst and blue-light irradiation, arylphosphines can be both alkylated and arylated using commercially available organohalides. In addition, the same organocatalyst can be used to transform white phosphorus (P4) directly into symmetrical aryl phosphines and phosphonium salts in a single reaction step, which has previously only been possible using precious metal catalysis.

Ln(ii) amido complexes coordinated by ring-expanded N-heterocyclic carbenes-promising catalysts for olefin hydrophosphination

First Ln(ii) ring-expanded NHC complexes (er-NHC)Ln[N(SiMe3)2]2 (Ln = Sm, Yb) are synthesized and proved to be highly efficient pre-catalysts for the intermolecular hydrophosphination of such indolent substrates as 1-alkenes, cyclohexene and norbornene. This journal is

Thermally Stable Ln(II) and Ca(II) Bis(benzhydryl) Complexes: Excellent Precatalysts for Intermolecular Hydrophosphination of C-C Multiple Bonds

A series of Ln(II) and Ca(II) bis(alkyl) complexes with bulky benzhydryl ligands, [(p-tBu-C6H4)2CH]2M(Ln) (M = Sm, L = DME, n = 2 (1); M = Sm, Yb, Ca, L = TMEDA, n = 1 (2, 3, 4), were synthesized by t

Calcium Amido Complexes Coordinated by Tridentate Amidinate Ligands: Synthesis, Structures and Catalytic Activity in Olefin Hydrophosphination and Polymerization of Cyclic Esters

The reactions of [(Me3Si)2N]2Ca(thf)2 with amidines 2-(Ph2P=NPh)C6H4NHC(tBu)=N(2,6-R2C6H3) {R = iPr (L1H); R = Me (L2H)} af

Amido Ca and Yb(II) Complexes Coordinated by Amidine-Amidopyridinate Ligands for Catalytic Intermolecular Olefin Hydrophosphination

A series of amido Ca and Yb(II) complexes LM[N(SiMe3)2](THF) (1Yb, 1-4Ca) coordinated by amidine-amidopyridinate ligands L1-4 were synthesized via a transamination reaction between proligands L1-4H and bisamido complexes M[N(SiMe3)2]2(THF)2 (M = Yb, Ca). The reactions of Yb[N(SiMe3)2]2(THF)2 with proligands L2H-L4H containing CF3 and C6H4F fragments do not allow for preparing the target Yb(II) complexes, while the Ca analogues were synthesized in good yields. Complexes 1Yb and 1-4Ca were evaluated as precatalysts for hydrophosphination of styrene, p-substituted styrenes, α-Me-styrene, and 2,3-dimethylbutadiene with various primary and secondary phosphines (PhPH2, 2,4,6-Me3C6H2PH2, 2-C5NH4PH2, Ph2PH, Cy2PH). Complexes 1Yb, 1-4Ca performed high catalytic activities in styrene hydrophosphination with PhPH2 and Ph2PH and demonstrated high regioselectivity affording exclusively the anti-Markovnikov addition products. For primary PhPH2 the reactions (1:1 molar ratio of substrates) catalyzed by 1Yb, 1Ca, and 2Ca proved to be highly chemoselective affording the secondary phosphine Ph(PhCH2CH2)PH; however, complexes 3Ca and 4Ca led to the formation of both secondary and tertiary phosphines in 80:20 and 86:14 ratios. Styrene hydrophosphinations with 2,4,6-Me3C6H2PH2 and 2-pyridylphosphine for all complexes 1Yb and 1-4Ca proceeded much more slowly compared to PhPH2. Addition of 2-C5NH4PH2 to styrene catalyzed by complex 1Yb turned out to be non-regioselective and led to the formation of a mixture of Markovnikov and anti-Markovnikov addition products, while all Ca complexes enabled regioselective anti-Markovnikov addition. Complexes 1Ca and 1Yb containing catalytic centers featuring similar ionic radii performed different catalytic activity: the ytterbium analogue proved to be a more active catalyst for intermolecular hydrophosphination of styrene with Cy2PH, 2-C5NH4PH2, and PhPH2, but less active with sterically demanding 2,4,6-Me3C6H2PH2. Styrenes containing in p-position electron-donating groups (Me, tBu, OMe) performed with noticeably lower rates in the reactions with PhPH2 compared to styrene. Complexes 1Yb, 1Ca, 2Ca, 3Ca, and 4Ca enabled addition of PhPH2 toward the double C-C bond of α-Me-styrene, and the reaction rate for this substrate is noticeably lower; however quantitative conversions were reached in -40 h. Complexes 1Ca and 2Ca promoted 1,2-addition of PhPH2 to 2,3-dimethyl butadiene with excellent regio- and chemoselectivity to afford linear secondary phosphines. Hydrophosphination of inert 1-nonene with Ph2PH with 40% conversion becomes possible due to the application of complex 2Ca (40 h, 70 °C). The rate law for the hydrophosphination of styrene with Ph2PH catalyzed by 1Ca was found to agree with the idealized equation: v = k[styrene]1[1Ca]1.

Hydrophosphination of alkenes and alkynes with primary phosphines catalyzed by zirconium complexes bearing aminophenolato ligands

Zirconium complexes stabilized by amine-bridged bis(phenolato) ligands showed good activity and chemo-selectivity in catalyzing intermolecular hydrophosphination of C-C multiple bonds with primary phosphines under mild conditions. A broad range of alkenes

Amino Ether-Phenolato Precatalysts of Divalent Rare Earths and Alkaline Earths for the Single and Double Hydrophosphination of Activated Alkenes

A range of stable ytterbium(II) amino ether-phenolato amido complexes of the type {LONxOy}Yb{N(SiMe3)2}, together with a congeneric samarium(II) and two calcium and strontium amido and alkyl derivatives, have been synthesized. They constitute very active, fully regioselective (anti-Markovnikov), and chemoselective precatalysts for the intermolecular hydrophosphination of styrene derivatives with PhPH2, achieving TONs up to 2150, TOFs up to 30 h-1 and chemoselectivities in the region of 95-99%. The ytterbium(II) precatalysts, among which is most prominently {LONO4}Yb{N(SiMe3)2} (3), where the ligand possesses a 15-c-5-aza-crown ether side arm, outperform their related calcium analogues, and the activity of the catalyst increases substantially with the denticity of the ligand. The rate law rate = k[p-tBu-styrene][3] was established following kinetic monitoring of the hydrophosphination of p-tBu-styrene and PhPH2 catalyzed by 3. The kinetic studies also revealed that the reactions are entropically driven and that reaction rates increase when electron-withdrawing groups are introduced at the para position of the styrenic substrate. It is proposed that these catalyzed hydrophosphination reactions proceed by rate-limiting olefin insertion into the [Yb]-phosphide bond. The chemoselective one-pot, two-step double hydrophosphination of PhPH2 with 2 equiv of styrene yields tertiary phosphines. It obeys an unusual kinetic profile where formation of the tertiary phosphine starts only when complete consumption of PhPH2 is first ensured. This sequence was used to obtain asymmetric tertiary phosphines with excellent selectivity.

A Study of Two Highly Active, Air-Stable Iron(III)-μ-Oxo Precatalysts: Synthetic Scope of Hydrophosphination using Phenyl- and Diphenylphosphine

The importance of phosphines in synthetic chemistry cannot be underestimated. Catalytic hydrophosphination offers an ideal method to prepare P?C bonds without the need for harsh reaction conditions or stoichiometric amounts of waste by-product. We herein report our studies into two biocompatible iron(III) complexes in hydrophosphination chemistry using diphenylphosphine under mild and benign reaction conditions (room temperature, solvent-free) and our extended exploration of hydrophosphination with phenylphosphine, which can be tuned to operate in the absence of catalyst under thermal conditions for single hydrophosphination or solvent-free with an iron(III) precatalyst to generate the products of double hydrophosphination. (Figure presented.).

Highly Active, Chemo- and Regioselective YbII and SmII Catalysts for the Hydrophosphination of Styrene with Phenylphosphine

Stable heteroleptic amido YbII and SmII complexes bearing aminoether-phenolate ligands and devoid of coordinated solvent have been structurally characterized. They afford highly active, chemoselective and, in the case of monoaddition

Metallacyclic yttrium alkyl and hydrido complexes: Synthesis, structures and catalytic activity in intermolecular olefin hydrophosphination and hydroamination

Metallacyclic neutral and ionic yttrium alkyl complexes coordinated by a dianionic ene-diamido ligand ([2,6-iPr2C6H3NC(Me) = C(Me)NC6H3iPr2-2,6] = L1) [L1]Y(CH2SiMe3)(THF)2 (2), {[L1]Y(CH2SiMe3)2}-{Li(THF)4}+ (3), [L1]Y(OEt2)(μ-Me)2Li(TMEDA) (4) were synthesized using a salt-metathesis approach starting from the related chloro complex [L1]Y(THF)2(μ-Cl)2Li(THF)2 (1) in 70, 85 and 72% yields respectively. The reactions of 2 with H2 or PhSiH3 afford the dimeric hydride {[L1]Y(THF)(μ-H)}2(μ-THF) (5) containing two μ-bridging hydrido and one μ-bridging THF ligands (91 and 85% yields). The X-ray studies of complexes 2, 3 and 5 revealed η2-coordination of the C = C fragment of an ene-diamido ligand to a Y cation. DFT calculations were carried out to give an insight into the metal-ligand bonding and especially the interaction between the metal and the ene-diamido ligand. The observed bonding of the ene-diamido fragment is found to reflect the acidity of the metal center in the complex that is partially overcome by a better donation from the double bond (better overlap with an empty d orbital at the yttrium center). The treatment of complex 4 with DME resulted in the C-O bond cleavage of DME and afforded a three nuclear methoxide oxide complex [{[L1]Y}3(μ2-OMe)3(μ3-O)]2-[Li(DME)3]+2 (6). Complexes 2, 3, 5 and 7 proved to be efficient precatalysts for the intermolecular hydrophosphination of styrene, 4-vinylpyridine, and 1-nonene with PhPH2 and Ph2PH as well as hydroamination of styrene and pyrrolidine.