Über die Umsetzung von Tris(dimethylamino)phosphin,Triisopropylphosphin und tButyldifluorphosphin mit tertiären Alkylaziden: Phosphazidbildung versus Phosphinimidbildung. Röntgenstrukturen von Triphenylmethylazid und Tris(dimethylamino)-N-triphenylmethylphosphazid

Reaction of Tris(dimethylamino)phosphine, Triisopropylphosphine and ^tButyldifluorophosphine with Tertiary Alkyl Azides: Phosphazide Formation versus Phosphinimide Formation. X-Ray Crystal Structures of triphenylmethylazide and Tris(dimethylamino)-N-triphenylmethyl Phosphazide Tris(dimethylamino)-phosphine and triisopropylphosphine react with tertiary alkyl azides RN₃ (R = ^tBu, 1-Ad, Trt) to give the corresponding phosphazides 1a–1c and 2a–2c , which involve a linear PN₃R-unit. The coordination geometries of the N₃ chains in triphenylmethylazide and 1c are completely different, associated with a change of hybridisation. Hence, the N₃-group of the triphenylmethylazide is nearly linear, whereas that of 1c shows approximately tetrahedral angles. The coordination geometry at the central nitrogen atom also depends on the substituents, possibly because of their varying ability to delocalize the π-electron system. In contrast, the reaction of ^tbutyldifluorophosphine with the same azides RN₃ led to the ^tbutyldifluorophosphinimides 3a–3c of the type ^tBuP(:NR)F₂. The hydrolysis of these compounds afforded the ^tbutylphosphonamidic fluorides ^tBuP(:O)(NHR)F (R = 1-Ad: 4b , Trt: 4c ), instead of the expected substitution products ^tBuP(:NR)(OH)F.     

Zinn(II)-halogenid-Komplexe mit Tri-tert-butylphosphin und Tris(dimethylamino)phosphin

Tin(II) Halide Complexes with Tri-tert-butylphosphine and Tris(dimethylamino)-phosphine TIn(II) chloride and tin(II) bromide react with tri-tert-butylphosphine and with tris(dimethylamino)phosphine to give stable 1:1 adducts. Infrared and raman data as well as¹H-n.m.r., ³¹P-n.m.r., and ^119mSn-Mössbauer spectra of the novel phosphine dihalogennostannylenes are discussed in terms of an ylidic type of bonding.     

A general synthesis of optically active phosphines,phosphinites and thiophosphinites from alkylthio(alkylseleno)phosphonium salts and tris(dimethylamino)phosphine as a thiophilic agent

Tris(dimethylamino)phosphine was found to be a suitable thiophilic reagent which converts optically active alkylthio(alkylseleno)phosphonium salts into chiral tertiary phosphines and phosphinites with a high stereoselectivity. The first synthesis of optically active thiophosphinites from bis(alkylthio)phosphonium salts and tris(dimethylamino)phosphine is also reported.     

Action du Tris(Diméthylamino)phosphine et de l'Oxyde de P,P-dichlorophenylphosphine sur les N 1Tosylamidrazones: Obtention des 3-(Dimethylamino) 1,2,4,3-triazaphospholines et des 3-Oxo1,2,4,3-triazaphospholines

The reaction of N¹-tosylamidrazones with tris(dimethylamino)phosphine and P,P-dichlorophenylphosphine oxide provides respectively a convenient access to the new 3-(dimethylamino)-1,2,4,3-triazaphospholines and 1,2,4,3-triazaphosphlines-3-oxide. The structure of all obtained products is confirmed by NMR (¹ H, ³¹ P, ¹³C) and IR spectroscopy.     

Intermediate carbene formation in the reaction of thioamides with phosphorus (III) derivatives: Quantum chemical investigation

The reactions of perfluoroalkyl thioamides with trimethyl phosphine, trimethyl phosphite, and tris(dimethylamino)phosphine have been analyzed by means of quantum chemical (DFT and MP2) calculations. The reaction seems to proceed via the nucleophilic attack of the electrophilic carbon atom by the phosphorus lone pair with the formation of cyclic or acyclic adducts. The latter releases the thiophosphate molecule forming perfluoroalkylaminocarbene as the short‐lived intermediate. The reaction of the carbene with the second molecule of trialkyl phosphite yields phosphorus ylide. The ylide undergoes a migration of fluorine from carbon to phosphorus. The reactions of perfluoroalkyl thioamides with phosphines and tris(dimethylamino)phosphine probably proceeds differently. Using alkyl thioamides or amides instead of perfluoroalkyl thioamides also makes the reaction less favorable. The only combination of perfluoroalkyl thioamides with trialkyl phosphite fulfills both the kinetic requirements (moderate activation energies and relative energies for intermediates) and the thermodynamic aspects (higher stabilities of the reaction products compared with the starting materials). © 2013 Wiley Periodicals, Inc.     

Reaktionen von Aminoboranen und Hydrazinoboranen mit Carbonyl- und Thiocarbonylverbindungen

Zusammenfassung Bei der Aminoborierung von Carbonylsulfid erfolgt 1,2-Addition an die Carbonylgruppe, wobei in Tris(dimethylamino)boran zwei der B–N-Bindungen, in Bis(dimethylamino)chlorboran nur eine B–N-Bindung reagieren. In Tris(2,2-dimethylhydrazino)boran reagieren alle drei B–N-Bindungen mit CO₂; mit CS₂ erfolgt unter den gleichen Bedingungen keine Reaktion. Mit Phosgen und Thiophosgen reagiert Tris(dimethylamino)boran unter Bildung von Bis(dimethylamino)chlorboran und substituierter Carbamide.

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Reactions of aminoboranes and hydrazinoboranes with carbonyl and thiocarbonyl compounds

Upon aminoboration of carbonyl sulfide 1,2-addition to the carbonyl group is observed. In tris(dimethylamino)borane insertion into two of the B–N bonds occurs, while in bis(dimethylamino)chloroborane only one B–N bond reacts with OCS. In tris(2,2-dimethylhydrazino)borane all three B–N bonds react with CO₂, while with CS₂ no insertion reaction is observed under comparable conditions. Tris(dimethylamino)borane reacts with phosgene and thiophosgene with formation of bis(dimethylamino)chloroborane and substituted carbamides.

     

Acyl- und Alkylidenphosphane. XVII. Triacetylphosphan aus Tris(trimethylsilyl)phosphan

Acyl- and Alkylidenephosphines. XVII. Triacetylphosphine from Tris(trimethylsilyl)-phosphine Tris(trimethylsilyl)phosphine reacts at 0°C with excess acetyl chloride in cyclopentane to form chlorotrimethylsilane and triacetylphosphine 3a . In contrast to the corresponding 2,2-dimethylpropionyl derivate (Z)- 5b the intermediate compounds (E)- and (Z)-acetyl-[1-(trimethylsiloxy)ethylidene]phosphine 5a are thermally instable. They could not be isolated in a pure state, but were characterized by NMR spectroscopic methods only. The isomers differ scarcely in their chemical shift values, but very much in their coupling constants. If the solution is cooled unsufficiently diacetyl-[1-(trimethylsiloxy)vinyl]phosphine 7 and the keto-enol-tautomers of diacetylphosphine K-/E- 2a are formed to a greater extend. ¹H-{³¹P}-INDOR experiments allowed the correlation between ¹H- and ³¹P-NMR resonances and hence the correct identification of the phosphines formed. Within days the compounds 2a and 7 also react at +20°C with an excess of acyl halide to give triacetylphosphine 3a .     

Bildung und Eigenschaften von Acylphosphinen. II. Verbindungen aus der Reaktion von Tris(trimethylsilyl)phosphin mit Pivaloylchlorid

Syntheses and Properties of Acylphosphines. II. Compounds from the Reaction of Tris(trimethylsilyl)phosphine with Pivaloyl Chloride Tris(trimethylsilyl)phosphine reacts with pivaloyl chloride at +20°C in cyclopentane to form the enol form of pivaloylbis(trimethylsilyl)phosphine. In this compound one trimethylsilyl group is bound to phosphorus, the other to oxygen. As the n.m.r. spectra of the reaction at ?10°C in monoglyme show the thermally instable keto form with two trimethylsilyl groups bound to phosphorus is formed first and rearranges at slightly elevated temperatures. Substitution of the second trimethylsilyl group yields the enol form of dipivaloyltrimethylsilylphosphine. Tripivaloylphosphine with three acyl groups bound to phosphorus and the enol form of tert. butylpivaloyltrimethyl-silylphosphine are produced in side reactions.     

Organophosphorus chemistry. Part 21 [1]. Insertion of olefins into P  CF3 bonds

Tris(trifluoromethyl)phosphine and ethylene reacted efficiently under u.v. irradiation to give 3,3,3-trifluoropropylbis(trifuomothyl) phosphine in good yield. With vinyl fluoride, vinylidene fluoride, and propene the reaction was regioselective rather than regiospecific, and the yield of 1:1 adduct was low. In these reactions, and in those with vinyl chloride, but-1-ene, and hexafluoropropene, in which only traces of 1:1-adduct could be detected, the bulk of the olefin and of the phosphine was recovered, and numerous by-products consistent with radical intermediates were identified. With propyne, 1,1,1-trifluoro-3-bis(trifluoromethyl)phosphino-cis-but-2-ene was obtained in moderate yield, but no reaction occurred between the phosphine and either but-2-yne or hexafluorcbut-2-yne. Tris(trifluoromethyl)phosphine oxide did not form an adduct with ethylene, tetrafluoroethylene, or propyne.Bis(trifluoromethyl)phosphine and dimethylphosphine both reacted readily under u.v. irradiation with 3,3,3-trifluoropropene, the phosphinyl radical attacking the terminal carbon in each case.     

Chelate von Chinolin-8-ol — Derivaten. XI. Eigenschaften und Struktur von Nickelchelaten alkyl-substituierter Chinolin-8-ole bzw. Chinolin-8-thiole

Reactions of 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete with N? H and P? H Acidic Compounds 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , reacts with aniline to give by opening of the ring 2,2,4,4-tetrakis(dimethylamino)-1-phenyl-1,2λ⁵,4λ⁵-azadiphosphapenta-1,3-diene, 2 , with p-CN? C₆F₄? NH₂ the product is 1-(4-cyano-2,3,5,6-tetrafluorophenyl)-2,2,4,4-tetrakis(dimethylamino)-1,2λ⁵,4λ⁵-azadiphosphapenta-1,3-diene, 3 . t-Butylamine or diethylamine do not react with 1 . Mesitylphosphane opens the ring system 1 forming by reduction of one phosphorus atom {[bis(dimethylamino)phosphanyl]methylidene}bis(dimethylamino)methylphosphorane, 4 . The same product 4 is obtained by reaction with phenylphosphane. The reaction products 2–4 are characterized by their nmr, mass, and ir spectra. Their way of formation is discussed. In 4 a ⁵J(PH), in 3 a ⁷J(CF) long range coupling constant could be identified.     

Umsetzung von N-Trimethylmetall(IVb)-trialkylphosphiniminen mit Halogenwasserstoffen

Reaction of N-Trimethylmetal(IVb) Trialkylphosphine Imines with Hydrogen Halides Investigations of the reaction of N-trimethylmetal(IVb)-substituted phosphine imines with hydrogen have been carried out. With one mole of HX phosphonium halides of the general formula [R₃P? NH? MMe₃]^⊕X^? (R = CH₃, C₂H₅; M = Si, Ge, Sn; X = Cl, Br, J) are obtained. A second mole of HX causes M? N bond cleavage, yielding aminophosphonium halides, [R₃P? NH₂]^⊕X^?.     

Reactions of Tris(diethylamino)phosphine with Some Quinones

Abstract

Tris(diethylamino)phosphine reacts with chloranil and 2,3-dichloro-4,5-dicyanoquinone to give products of addition to carbon with loss of chloride ion.     

Synthesis and coordination properties of new preorganized ligand on the triphenylphosphine oxide platform

Tris(2-cyanomethoxyphenyl)phosphine oxide was synthesized by the reaction of tris-(2-hydroxyphenyl)phosphine oxide with chloroacetonitrile. Its coordination properties were studied for the complexation with neodymium(iii) and copper(ii) nitrates using vibrational spectroscopy, NMR, and quantum chemical calculations.     

Study of the reaction of methyltris(dimethylamino)silane with diamines

Tris(dimethylamino)methylsilane reacts with N,N′-dialkyldiamines to give the corresponding substituted 1,3,2-diazasilacycloalkanes. In contrast, the reaction with an N-alkyldiamine yields the corresponding polycyclic silazane.     

Tris(Trimethylsilyl)Phosphine in Reaction with Bis(Phenylenedioxa)Chlorophosphorane. The Way to Phosphoranylphosphines

Abstract

Tris(trimethy1silyl)phosphine (1) is the key reagent in the synthesis of one- and two-coordinated phosphorus compounds. Its characteristic features are extreme reactivity, high nucleophility of phosphorus atom and the P-Si bonds lability. The interaction of phosphine (1) with bis(catecho1)chlorophosphome (2) has been studied by dynamic ³¹P NMR method. On the reagents ratio 1:1 at first the nucleophilic substitution of chlorine occurs leading to formation of phosphome (3) with P^III-P^v bond (σ_P(III) -117.0, σ^P(V) 17.4 ppm, ¹J_pp 305.0 Hz) which converts then into more stable 2-(trimethylsiloxyphenyloxy)-4,5-bem- 1,3,2-dioxaphospholane (4).     

Ein (Phosphonioalkinyl)- und ein Acetyl(tetracarbonyl)eisen

A (Phosphonioalkinyl)- and an Acetyl(tetracarbonyl)iron From the reaction of 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , and Fe(CO)₅ {[bis(dimethylamino)phosphoryl-methyl]-bis(dimethylamino)phosphonioethinyl}(tetracarbonyl)iron, 4 , and {1,1,3,3-tetrakis(dimethylamino)-1,4-dihydro- 1λ⁵,3λ⁵-[1,3]diphosphetium-2-carbonyl}(tetracarbonyl)-iron, 5 , can be isolated as crystalline products. The nmr, mass and ir spectra of the two compounds as well crystal and molecular structures of 4 are reported. The bonding situation in compounds 4 and 5 are discussed in detail.     

Tris(tetramethylguanidinyl)phosphine: The Simplest Non-ionic Phosphorus Superbase and Strongly Donating Phosphine Ligand

We report the synthesis and properties of the much sought-after tris(1,1,3,3-tetramethylguanidinyl) phosphine P(tmg)₃, a crystalline, superbasic phosphine accessible through a short and scalable procedure from the cheap and commercially available bulk chemicals 1,1,3,3-tetramethylguanidine, tris(dimethylamino)-phosphine and phosphorus trichloride. The new phosphine exhibits exceptional electron donor properties and readily forms transition metal complexes with gold(I), palladium(II) and rhodium(I) precursors. The formation of zwitterionic Lewis base adducts with carbon dioxide and sulfur dioxide was explored. In addition, the complete series of phosphine chalcogenides was prepared from the reaction of P(tmg)₃ with N₂O and the elemental chalcogens.     

Sterically Crowded Tris(2-(trimethylsilyl)phenyl)phosphine – Is it Still a Ligand?

Tris(2-(trimethylsilyl)phenyl)phosphine, P(o-TMSC₆H₄)₃, was synthesised and characterised in solution and in the solid state. The large steric bulk prevents most reactions of the phosphorus donor and makes the compound air stable both in the solid state as well as in solution. This shielded phosphine can still undergo three reactions, namely protonation, oxidation to the phosphine oxide under harsh conditions and complexation to Au^I, thus forming a complex with linear coordination. Unexpectedly, complexation was unsuccessful with a range of other metal cations. Neither Pd^II, Pt^II, Zn^II nor Hg^II reacted and even the remaining coinage metal cations Cu^I and Ag^I could not be coordinated. Both the parent molecule as well as the reaction products were structurally characterised by single crystal X-ray diffraction, and the conformational change of geometry required to accommodate the additional atoms was analysed in detail. Apart from chemical oxidation with H₂O₂, P(o-TMSC₆H₄)₃ displays reversible electrochemical oxidation with a potential not unlike the one of sterically unencumbered phosphines for which the oxidation is usually not reversible. P(o-TMSC₆H₄)₃ can thus be considered a model compound for the investigation of the electronic properties of sterically unencumbered phosphines.     

Reactions of bis(trifluoromethyl)nitroxyl with tris(pentafluorophenyl)-phosphine arsine and stibine

Tris(pentafluorophenyl)phosphine is oxidised by bis(trifluoromethyl)nitroxyl to form tris(pentafluorophenyl)phosphine oxide and perfluoro(2,4-dimethyl-3-oxa-2,4-diazapentane). With the corresponding arsine and stibine, addition products are obtained, namely tris(pentafluorophenyl)-arsenicdi[bis(trifluoromethyl)nitroxide] and tris(pentafluorophenyl)-antimonydi[bis(trifluoromethyl)nitroxide] respectively. Some reactions of the new derivatives are described.     

Reaction of N‐thioamido amidines with phosphoramide derivatives: Synthesis of 2‐substituted‐1,3,5,2‐triazaphosphorines

The reaction of N‐thioamido amidines 1 with tris(dimethylamino)phosphine or bis(diethylamino)phenylphosphine in refluxing toluene leads to the 1,3,5,2λ³‐triazaphosphorines 2 and 3 , respectively. The condensation results in the release of two molecules of dialkylamine. The sulfuration of the trivalent phosphorus atoms was achieved by the reaction with elemental sulfur, followed by heating in toluene. The structure of the triazaphosphorines 2 and 3 and their thione derivatives 4 and 5 were readily elucidated by means of ¹H, ¹³C, and ³¹P NMR spectroscopy and mass spectrometry. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:272–277, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20546