Primary Alkylphosphines Research Articles

A Simple Manganese(I) Catalyst for the Efficient and Selective Hydrophosphination of Olefins with PH3, Primary, and Secondary Phosphanes.

A tridentate ligand L with a P,NH,N donor motif was synthesized in few steps from commercially available precursors. Upon reaction with [MnBr(CO)5], an octahedral 18-electron complex [Mn(CO)3(L)]Br (1) is obtained in which L adopts a facial arrangement. After deprotonation of the NH group in the cationic complex unit, a neutral Mn(I) amido complex [Mn(CO)2(L-H)] (2) is formed under loss of CO. Rearrangement of L-H leads to a trigonal bipyramidal structure in which the P and N donor centers are in trans position. Further deprotonation of 2 results in a dep-blue anionic complex fragment [Mn(CO)2(L-2H)]- (3). DFT calculations and a QTAIM analysis show that the amido complex 2 contains a Mn-N bond with partial double bond character and 3 an aromatic MnN2C2 ring. The anion [Mn(CO)2(L-2H)]- reacts with Ph2PH to give a phosphido complex, which serves as phosphide transfer reagent to activated olefins. But the catalytic activity is low. However, the neutral amido complex 2 is an excellent catalyst and with loadings as low as 0.04 mol %, turn over frequencies of >40'000 h-1 can be achieved. Furthermore, secondary and primary alkyl phosphines as well as PH3 can be added in a catalytic hydrophosphination reaction to a wide range of activated olefins such as α,β-unsaturated aldehydes, ketones, esters, and nitriles. But also, vinyl pyridine and some styrene derivatives are converted into the corresponding phosphanes.

Transition metal mediated routes to poly(arylphosphine)s: investigation of novel phosphorus containing conjugated polymers

Poly(aryl- P-alkylphosphine)s were prepared via palladium and nickel mediated coupling and the spectral and electrochemical properties of the polymers were investigated. Palladium catalyzed carbonphosphorus bond formation was used for the preparation of poly( p-phenylene- P-alkylphoshpine)s ( 1a– b) via two routes. Low molecular weight polymers (1000–3000) were obtained by the condensation polymerization of 1,4-diiodobenzene with primary alkylphosphines. Higher molecular weight polymers (1000–14 000) were obtained via polymerization of p-bromophenylalkylphosphines ( 2a– b). Poly(4,4′-diphenyl- P-2,4,4-trimethylpentylphosphine (TMPPH 2)) ( 4b) was also prepared via two routes, the palladium catalyzed cross-coupling of 4,4′-diiodobiphenyl with primary alkylphosphines and the nickel mediated homo-coupling of bis- p-bromophenylalkylphosphines. The molecular weight of 4b was low (1000–3000) via both routes due to poor solubility. The electronic properties of polymers 1a– b were investigated with UV–vis–NIR spectroscopy and cyclic voltammetry and suggest a degree of electronic delocalization along the polymer backbone through phosphorus.

Thermochemistry of heteroatomic compounds. Part 12. The theoretical calculation of vaporization and solvation enthalpies for primary alkylphosphines and alkylendiphosphines

Abstract The theoretical calculations of vaporization and solvation enthalpies for primary alkylphosphines and alkylendiphosphines have been presented in this report. The calculations of the first from the above mentioned thermochemical therms were performed with the use of Trouton's and Wadso's equations. The obtained data allowed us to calculate the H 2 P-group contribution (16.0 ± 1.2 kJ mol −1 ) into vaporization enthalpies for the similar class of high-molecular alkylphosphines and alkylendiphosphines. − Enthalpies of non-specific solvation were obtained in accordance with the general equation Δ H solv = a s + b s MR D obtained previously for the estimation of the non-specific solvation enthalpy of P(III)-containing compounds in following solvents: carbon tetrachloride, benzene ρ-xylene, methanol and pyridine.

ChemInform Abstract: Cleavage of P‐P Bonds in Phosphorus. An Efficient Method for the Preparation of Primary Alkylphosphines.

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Cleavage of P[sbnd]P Bonds in Phosphorus. An Efficient Method for the Preparation of Primary Alkylphosphines

Effective cleavage of P P bonds in red (and yellow) phosphorus can be brought about by adding tert -butyl alcohol to a mixture of phosphorus, lithium and liquid ammonia; subsequent addition of alkyl halides gives primary phosphines in good to excellent yields.

New zirconium phosphido complexes and their reactions with alkenes

The reaction of PH3 with the bispentamethylcyclopentadienyl zirconium dinitrogen complex [{Zr(C5Me5)2(N2)}2(µ-N2)]1 produces the orange and the yellow phosphido complexes [{Zr(C5Me5)2(PH2)(H)}2(µ-N2)]2 and [{Zr(C5Me5)2(PH2)(H)}2]3; the reaction of these complexes with alkenes and PH3 leads to the selective formation of primary alkyl phosphines, under the mildest conditions of temperature and pressure reported to date.

ChemInform Abstract: One‐Step Synthesis of 1,4‐Dialkyl‐1,4‐diphospha‐2,3,5,6‐tetrahydroxycyclohexanes from Primary Alkylphosphines and Glyoxal.

ChemInformVolume 21, Issue 44 Organoelement Compounds ChemInform Abstract: One-Step Synthesis of 1,4-Dialkyl-1,4-diphospha-2,3,5,6-tetrahydroxycyclohexanes from Primary Alkylphosphines and Glyoxal. A. J. ROBERTSON, A. J. ROBERTSON Cyanamid Canada Inc., Niagara Falls, Ontario L2E 6T4, CanadaSearch for more papers by this author A. J. ROBERTSON, A. J. ROBERTSON Cyanamid Canada Inc., Niagara Falls, Ontario L2E 6T4, CanadaSearch for more papers by this author First published: October 30, 1990 https://doi.org/10.1002/chin.199044229AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume21, Issue44October 30, 1990 RelatedInformation

One Step Synthesis of 1,4-Dialkyl-1,4-Diphospha 2,3,5,6-Tetra -Hydroxycyclohexanes from Primary Alkylphosphines and Glyoxal

Abstract High yields of 1,4-dialkyl 1,4-diphospha 2,3,5,6 tetrahydroxycyclohexanes are produced when equal molar portions of glyoxal are added to primary alkylphosphines. The reactions take place at low temperatures and without the aid of an acid catalyst. The cyclic products are readily converted to the corresponding 1,4 diphosphoryl or dithiophosphoryl derivatives with the addition of a slight excess of H2O2 or sulphur. Of particular importance are the order and rates of addition of the two reagents. Reversal of the addition of the reagents results in an entirely different product. This synthesis offers an easy route to 1,4-diphosphacyclohexanes. In addition, the oxides of the lower homologs have utility as flame retardants for polymethymethacrylate and other plastics.

An NMR study of the reactions of primary alkylphosphines, arsines and stibines with disulfur dichloride

An NMR study of the reactions of primary alkylphosphines, arsines and stibines with disulfur dichloride

Reactions of alkylphosphorus, arsenic, and antimony hydrides and halides with dibenzylmercury. An improved procedure for cyclopolyarsines

Dibenzylmercury is a convenient and general reagant for the formation of homoatomic catenates from primary alkyl phosphines, arsines and stibines. From CH 3PH 2, CH 3AsH 2 and C 2H 5AsH 2, the products are Hg o and the cyclopentamers, (CH 3P) 5, (CH 3As) 5 and (C 2H 5As) 5, respectively. From CH 3SbH 2, the solid, polymeric product, (CH 3Sb) x , is obtained. With (CH 3) 2AsH, both the condensation product, (CH 3) 2AsAs(CH 3) 2, and the substitution product, (CH 3) 2AsCH 2C 6H 5, are obtained. With dibenzylmercury, CH 3PCl 2, CH 3AsCl 2, and CH 3SbCl 2 give only the monosubstitution product CH 3E(Cl)CH 2C 6H 5 (E = P, As or Sb) and HgCl 2. With CH 3AsI 2, disubstitution occurs giving (in addition to HgI 2) CH 3As(CH 2C 6H 5) 2, and with (CH 3) 2AsI, (CH 3) 2AsCH 2C 6H 5. In all cases the conversion of starting materials to the indicated products is very high.