Potassium Diphenylphosphide Research Articles

An unusual phosphide addition reaction of 1,3-dimethyl-1,2,3-benzotriazolium iodide

The reactivity of the stable N-heterocyclic nitrenium salt 1,3-dimethyl-1,2,3-benzotriazolium iodide (1) toward various nucleophilic reagents has been investigated. Strongly nucleophilic reagents such as potassium hydride (KH), potassium cyclopentadienide (KCp), potassium tert-butoxide (KOtBu), sodium methoxide (NaOMe), and sodium ethanethiolate (NaSEt) all reacted with 1 under demethylation and back-formation of 1-methyl-1,2,3-benzotriazole (2) in high isolated yield (ca. 80–90%). In marked contrast, an unusual phosphide addition reaction took place when 1 was treated with 1 equiv. of potassium diphenylphosphide (as the 1,4-dioxane adduct KPPh2(dioxane)2). In the course of this reaction the P atom replaces the central nitrogen of the triazole ring while being formally oxidized to an iminophosphorane derivative (3). Both compounds 2 and 3 have been structurally characterized through single-crystal X-ray diffraction.

Application of Tripodal Linker Units to Immobilized Diphenylphosphine Palladium Complex Catalysts for Suzuki-Miyaura Coupling Reactions of Aryl Bromide: Effect of Immobilization Method of Phosphine Ligand on Catalytic Performance

A tripodal linker unit that tightly binds to a silica surface via three independent Si–O–Si bonds was applied to immobilize diphenylphosphino-palladium complex catalysts onto ordered mesoporous silica. The diphenylphosphino-functionalized silica materials were prepared by: (i) grafting the bromine-substituted tripodal linker unit onto mesoporous silica and a subsequent treatment with potassium diphenylphosphide (the “bottom-up” method), (ii) directly grafting pre-synthesized tripodal diphenylphosphino ligands onto silica (the “top-down” method). The catalytic properties were evaluated in the Suzuki-Miyaura coupling reaction of aryl bromides. The tripodally immobilized catalyst prepared via the “bottom-up” method showed lower leaching levels of palladium and phosphorus compared to catalyst prepared via the “top-down” method.

Diphenylphosphino functionalization of mesoporous silica using tripodal linker units

The immobilization of diphenyl phosphine onto ordered mesoporous silicas using a tripodal linker unit possessing one bromopropyl group and three anchoring silicon atoms was investigated. Solid-state 31P, 29Si, and 13C cross-polarization/magic angle spinning (CP/MAS) NMR spectroscopic studies as well as isothermal nitrogen adsorption/desorption measurements revealed that grafting the tripodal linker unit and a subsequent reaction with potassium diphenylphosphide (the “bottom-up” method) successfully realized diphenylphosphino functionalization of silica while maintaining the mesoporous structure. In contrast, directly grafting tripodal diphenylphosphino ligands pre-synthesized from the tripodal linker unit onto silica (the “top-down” method) was unsuccessful.

Chemoselectivity control in the reaction of a dinuclear chloro-bridged cyclopalladated complex with potassium diphenylphosphide

Reactions of KPPh 2 with the dimeric cyclopalladated complex {Pd(N∩C)( μ-Cl)} 2 1 derived from N,N-dimethylbenzylamine were studied using different reagent ratios, temperature, reaction time, concentrations and solvents. Complex 3, the μ-Cl- μ-PPh 2 analog of 1, was obtained in 76% yield in the one-hour reaction using the 1:1 ratio of dimer 1 and KPPh 2 in THF at rt. ortho-(Diphenylphosphino)benzylamine 4 was synthesized in 58% yield by reacting complex 1 with 4.5 equiv. of KPPh 2 in THF at rt. A possible mechanism of the aminophosphine formation is proposed on the basis of the experimental data including 31P{ 1H} NMR spectra of reaction mixtures.

Novel method for the synthesis of diselenophosphinates

225 Alkali metal and organylammonium diseleno phosphinates are convenient precursors for semi conducting [1] and magneto optical [2] nanomate rials, ligands for designing metal complexes [3], promising extractants of rare and transuranium ele ments [4], potential biologically active compounds [5], and building blocks for organic synthesis [6]. At the same time, the known methods for their prepa ration are multistep and laborious and based on the use of toxic, corrosive, and not readily available compounds [1, 7–9]. For example, sodium diphe nyldiselenophosphinate was obtained as a solvate [Na(Se2PPh2) · THF · 5H2O] in low yield from chlorodiphenylphosphine, sodium metal, and ele mental selenium in liquid ammonia [9]. Similar potassium salt results as a monohydrate [К(Se2PPh2) · H2O] from the reaction of potassium diphenylphosphide (obtained by the cleavage of Ph3P with potassium metal K) with elemental sele nium [2]. Triethylammonium diphenyldiseleno phosphinate [Ph2PSe2][HNEt3] was isolated from a complex reaction mixture resulting from the treat ment of chlorodiphenylphosphine with a triethylsi lane–triethylamine system (ambient temperature, 6 h) followed by refluxing the reaction products with elemental selenium (toluene, 20 h) [1].

Synthesis, reactivity and molecular structure of phosphino tetramethyl cyclopentadienyl complex (η5: η1-C5Me4CH2PPh2)Re(CO)2

The fulvene complex (eta(6)-C(5)Me(4)CH(2))Re(C(6)F(5))(CO)(2) reacts at the exocyclic methylene carbon with potassium diphenylphosphide to yield the anionic species [(eta(5)-C(5)Me(4)CH(2)PPh(2))Re(C(6)F(5))(CO)(2)](-) (). Protonation of with HCl at 0 degrees C produces the hydride complex trans-(eta(5)-C(5)Me(4)CH(2)PPh(2))Re(C(6)F(5))(H)(CO)(2) (). Thermolysis of a hexanes solution of , under nitrogen atmosphere, produces the chelated complex (eta(5):eta(1)-C(5)Me(4)CH(2)PPh(2))Re(CO)(2) () in good yield. The thermolysis under a CO atmosphere affords a mixture of the complexes (eta(5):eta(1)-C(5)Me(4)CH(2)PPh(2))Re(CO)(2) () and (eta(5)-C(5)Me(4)CH(2)PPh(2))Re(CO)(3) (). The reaction of with two electron donor ligands yields (eta(5)-C(5)Me(4)CH(2)PPh(2))Re(CO)(2)(L) (, L = CO; , L = PMe(3); , L = (t)BuNC). Complex also reacts with I(2), HBF(4) and MeOTf to yield the cationic compounds trans-[(eta(5):eta(1)-C(5)Me(4)CH(2)PPh(2))Re(R)(CO)(2)](+) (, R = I; , R = H; , R = Me). Upon treatment with chloroform, the hydride complex converts to the corresponding chloro derivative . The trans stereochemistry for complexes have been assigned on basis of nu(CO) IR intensities and (13)C-NMR chemical shifts. The reaction of the cationic complexes (, ) with KI and Me(3)NO.2H(2)O yields the neutral species cis-(eta(5):eta(1)-C(5)Me(4)CH(2)PPh(2))Re(I)(R)(CO) (, R = I, , R = Me). The molecular structure of and have been determined by X-ray crystallography.

Improved and Efficient Synthesis of Chiral N,P-Ligands via Cyclic Sulfamidates for Asymmetric Addition of Butyllithium to Benzaldehyde

A robust and scaleable route to chiral 1-isopropylamino-2-(diphenylphosphino)ethanes is described via the ring-opening of chiral, cyclic sulfamidates with potassium diphenylphosphide (KPPh(2)). The novel protocol offers a robust access to gram quantities of chiral amino phosphinoethanes in high yields. The Li-amides of the chiral aminophosphines were evaluated as chiral ligands in the asymmetric addition of n-butyllithium (BuLi) to benzaldehyde, yielding 1-phenylpentanol up to 98% ee.

Chiral Phosphinophenyloxazolines Bearing Alkoxymethyl Substituents: Synthesis and Application in the Palladium Catalyzed Allylic Substitution Reactions

The chiral phosphine-oxazoline ligands 3 and 4 bearing 4-alkoxymethyl substituents on the oxazoline ring with (R)-configuration were prepared from L-serine methyl ester in 66% and 33% yields, respectively. Along this synthetic pathway, the β-hydroxylamides derived from L-serine methyl ester and 2-halobenzoyl chlorides were expediently converted to the corresponding oxazolines by using diethylaminosulfur trifluoride as the activation agent. Potassium diphenylphosphide was the reagent of choice for replacing the bromine atom on the phenyl ring, giving the desired oxazoline-phosphine ligands 3 and 4. Together with [Pd(η3-allyl)Cl]2, ligands 3 and 4 induced an enantioselective allylic substitution reaction of 1,3-diphenyl-2-pro-penyl acetate by dimethyl malonate. Although ligands 3 and 4 exhibit the (R)-configuration, differing from the (S)-configuration of Pfaltz-Helmchen-Williams phosphine-oxazoline ligands, all these ligands led to the same enantiotopic preference in the allylic substitution reaction. To facilitate the recovery and reuse of the phosphine-oxazoline ligand, immobilization on Merrifield resin was attempted, albeit in low loading.

Carbonylation of aryl halides catalyzed by a silica-supported sulfur and phosphine mixed bidentate palladium complex

A silica-supported sulfur and phosphine mixed bidentate palladium complex has been prepared from 4-thia-6-chlorohexyltrimethoxysilane via immobilization on fumed silica, followed by reacting with potassium diphenylphosphide in tetrahydrofuran (THF) and then the reaction with palladium chloride in acetone. This polymeric palladium complex is an efficient catalyst for Heck carbonylation of aryl halides with aniline or n-butyl alcohol under atmospheric pressure of carbon monoxide and can be recovered and reused without loss of activity.

Coordination chemistry of diselenophosphinate complexes: the X-ray single-crystal structures of [K(Se2PPh2)(THF)2]2 and [In(Se2PPh2)3].L (L = THF, PhMe).

Reaction of potassium diphenylphosphide with elemental selenium is shown to give [K(Se(2)PPh(2))(THF)(2)](2) 1, which further reacts with InCl(3) to yield [In(Se(2)PPh(2))(3)] 2. Crystallization of 2 from either THF or PhMe gave 2.THF or 2.PhMe, respectively, both of which form loosely linked dimers in the solid state via Se...Se intermolecular van der Waals interactions. Decomposition of 2 has been studied by TGA.

Induction of Planar Chirality in Formation of (η5:η1-1-(1-Cyclohexyl-2-(diphenylphosphino)ethyl)indenyl)carbonylrhodium and (η5:η1-1-(2-Phenyl-2- (diphenylphosphino)ethyl)indenyl)carbonylrhodium

The enantiopure bidentate indenyl-phosphine ligands (1S)-[2-(3H-inden-1-yl)-1-phenylethyl] diphenylphosphine (9) and [(2R)-2-cyclohexyl-2-(3H-inden-1-yl)ethyl]diphenylphosphine (18) were synthesized in 20% yield and three steps from (R)-styrene oxide and in 61% yield and four steps from vinylcyclohexane, respectively. In both cases ring opening of a spirocyclopropane-1,1'-indene with potassium diphenylphosphide was a key step. Addition of the lithium salts of 9 and 18 to [Rh(? -Cl)(CO)(2)](2) gave (?(5):?(1)-indenyl-CH2CH(Ph)PPh2)RhCO and (?(5):?(1)-indenyl-CH(Cy)CH2PPh2)RhCO as 75:25 and 78:22 mixtures of diastereoisomers, from which the major complexes were readily obtained by crystallization. The chiral centers in the linking chain ? and ? to the indenyl ring had thus induced good planar chirality of the complexed indenyl moiety. Both complexes were characterized by X-ray crystallography.

In Situ and Reactor Study of the Enantioselective Hydrogenation of Acetylacetone by Ruthenium Catalysis with the New Chiral Diphosphine Ligand (R)-(R)-3-Benzyl-2,4-bis(diphenylphosphino)pentane

The new optically pure C1-symmetric diphosphine ligand (R)-(R)-3-benzyl-2,4-bis(diphenylphosphino)pentane (BDPBzP) has been synthesized by enantioselective reduction of 3-benzyl-2,4-pentanedione with [((S)-BINAP)Ru(p-cymene)Cl]Cl, followed by the reaction of potassium diphenylphosphide with the bis(mesylate) intermediate (S)-(S)-PhCH2CH(CH(OMs)CH3)2. The Ru(II) complexes [(BDPBzP)Ru(p-cymene)I]I·2CH2Cl2 (5), [(BDPBzP)(DMSO)Ru(μ-Cl)3RuCl(BDPBzP)] (6a), and [(BDPBzP)RuCl(CH3CN)3]OTf (7) have been prepared and characterized by multinuclear NMR spectroscopy. The p-cymene complex 5 has been authenticated by a single-crystal X-ray analysis. All Ru(II) complexes are effective catalyst precursors for the enantioselective hydrogenation of acetylacetone to (R)-(R)-2,4-pentanediol. The best catalytic performance in terms of enantioselective discrimination (ee's up to 99%) has been observed for the dimer 6a. An in situ high-pressure NMR study in catalytic conditions has shown that the nonclassical polyhydride dimer [...

4,5-bis(diphenylphosphino)acridine: A new type of tridentate phosphorus-nitrogen-phosphorus ligands

Abstract Reaction of 4,5-difluoroacridine ( 8) with two equivalents of potassium diphenylphosphide (Ph 2PK) yielded the title compound 3. Contrarily, diphenylphosphine (Ph 2PH) reacted with 8 under addition, and 4,5-difluoro-9-diphenyl-9,10-dihydroacridine ( 12) was obtained. Compound 8 was prepared from 2-amino-3-fluorobenzoic acid ( 13) in a four step synthesis. As it is shown by the preparation of the metal complexes 4,5-bis(diphenylphosphino)-acridine-palladium dichloride ( 16) and 4,5-bis(diphenylphosphino)acridine-molybdenum tricarbonyl ( 17), compound 3 is capable of acting as a tridentate PNP ligand which coordinates transition metals in an approximately “T-shaped” planar coordination geometry. Single crystal X-ray structure analyses are reported for 3 and 17.

ChemInform Abstract: The Preparation of Functionalized Arylphosphines (III) from Aryl Fluorides (I) by Nucleophilic Aromatic Substitution with Potassium Diphenylphosphide (II).

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

New Organophosphorus Ligands: 1,1,4,4‐Tetrakis(diphenylphosphanyl)butatriene and Its Tetrasulfide

AbstractTreatment of bis(diphenylphosphanyl)ethyne with potassium diphenylphosphide in tetrahydrofuran leads to the formation of tetraphenyldiphosphane Ph2P–PPh2 and the title compound (Ph2P)2C=C=C=C(PPh2)2 (1). A mechanism is proposed for this process. Compound 1 reacts with elemental sulfur to give the tetrasulfide [Ph2(S)P]2C=C=C=C[P(S)Ph2]2 (2). The crystal structures of 1 and 2 have been determined by single‐crystal X‐ray diffraction. In both cases the linear butatriene unit shows strongly alternating C=C bond lengths as predicted in theoretical studies.

Investigation of the purity of alkali metal diphenylphosphides and their reactions with organic halides. Evidence for single electron transfer

For the first time the purity of lithium, sodium, and potassium diphenylphosphide, prepared by various methods, has been evaluated using 31 P NMR spectroscopy. A method was developed to prepare each of the phosphides in a high state of purity. Highly pure potassium diphenylphosphide was then allowed to react with p-iodotoluene in order to determine the effect of purity on the S RN 1 nature of this reaction. The results were then compared with literature reports which used less pure KPPh 2 . The mechanism of reaction of allyl halides with pure alkali metal diphenylphosphides, using the radical probes 6-halo-5,5-dimethyl-1-hexenes and 1-halo-2,2-dimethylhexanes, was investigated. The results provide the first evidence to support single electron transfer (SET) in the reaction of an alkali metal diphenylphosphide with an alkyl halide. SET was found to be the major reaction pathway in the reaction of hindered alkyl iodides (neopentyl type). On the other hand, SET was found to be minor pathway in the reaction of the corresponding alkyl bromides and chlorides with PPh 2 - . These was no evidence found for SET in the reactions of unhindrered alkyl halides with PPh 2 - although SET participation cannot be rigorously excluded

The Preparation of Functionalised Aryl Phosphines from Aryl Fluorides by Nucleophilic Aromatic Substitution with Potassium Diphenylphosphide

The Preparation of Functionalised Aryl Phosphines from Aryl Fluorides by Nucleophilic Aromatic Substitution with Potassium Diphenylphosphide

The title compound 4 was synthesized from dipotassium 1,8‐anthracenedisulfonate (9) and potassium diphenylphosphide (Ph2PK). On reaction of 4 with nickel(II) chloride and bis‐(benzonitrile)palladium(II) chloride, cyclometallation of the C – H bond in anthracene 9‐position led to the square‐planar chelate complexes 11 and 13, respectively. In the case of the palladium complex 13, the cyclometallated structure was proved by X‐ray structure

The title compound 4 was synthesized from dipotassium 1,8-anthracenedisulfonate and potassium diphenylphosphide (Ph 2 PK). On reaction of 4 with nickel(II) chloride and bis-(benzonitrile)palladium(II) chloride, cyclometallation of the C-H bond in anthracene 9-position led to square-planar chelate complexe

ChemInform Abstract: Stereoselective Reduction of gem‐Dichlorocyclopropanes by Potassium Diphenylphosphide.

ChemInform Abstract: Stereoselective Reduction of gem‐Dichlorocyclopropanes by Potassium Diphenylphosphide.

Stereoselective reduction of gem-dichlorocyclopropanes by potassium diphenylphosphide

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStereoselective reduction of gem-dichlorocyclopropanes by potassium diphenylphosphideGordon F. MeijsCite this: J. Org. Chem. 1987, 52, 17, 3923–3925Publication Date (Print):August 1, 1987Publication History Published online1 May 2002Published inissue 1 August 1987https://doi.org/10.1021/jo00226a039RIGHTS & PERMISSIONSArticle Views225Altmetric-Citations19LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (438 KB) Get e-Alerts Get e-Alerts