- Reactivity of bulky aminophosphanes towards small molecules: Activation of dihydrogen and carbon dioxide by aminophosphane/borane frustrated Lewis pairs
-
A series of mono- and bisaminophosphanes with formulas R2NPR'R’’ and (R2N)2PR’ (R = iPr, Cy; R’ = Ph, Cy; R’’ = iPr) were characterized by X-ray analysis, NMR spectroscopy and computational methods. The common structural f
- Chojnacki, Jaros?aw,Grubba, Rafa?,Kaniewska-Laskowska, Kinga,Siedzielnik, Magdalena,Szynkiewicz, Natalia
-
-
- A Mild One-Pot Reduction of Phosphine(V) Oxides Affording Phosphines(III) and Their Metal Catalysts
-
The metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum chemical calculations support the attack of the dissociated chloride anion of intermediated phosphonium salt at the silicon of the disilane as the rate-limiting step for deprotection. The exquisite purity of the resultant phosphine(III) ligands after the simple removal of volatiles under reduced pressure circumvents laborious purification prior to metalation and has permitted the facile formation of important transition metal catalysts.
- Kapu?niak, ?ukasz,Plessow, Philipp N.,Trzybiński, Damian,Wo?niak, Krzysztof,Hofmann, Peter,Jolly, Phillip Iain
-
supporting information
p. 693 - 701
(2021/04/06)
-
- Exploring the Reactivity of Donor-Stabilized Phosphenium Cations: Lewis Acid-Catalyzed Reduction of Chlorophosphanes by Silanes
-
Phosphane-stabilized phosphenium cations react with silanes to effect either reduction to primary or secondary phosphanes, or formation of P-P bonded species depending upon counteranion. This operates for in situ generated phosphenium cations, allowing catalytic reduction of P(III)-Cl bonds in the absence of strong reducing agents. Anion and substituent dependence studies have allowed insight into the competing mechanisms involved.
- Pearce, Kyle G.,Borys, Andryj M.,Clark, Ewan R.,Shepherd, Helena J.
-
p. 11530 - 11536
(2018/09/21)
-
- Cleavage of P=O in the presence of P-N: Aminophosphine oxide reduction with in situ boronation of the PIII product
-
In contrast to tertiary phos-phine oxides, the deoxygenation of aminophosphine oxides is effectively impossible due to the need to break the immensely strong and inert P=O bond in the presence of a relatively weak and more reactive P-N bond. This long-sta
- Kenny, Niall P.,Rajendran, Kamalraj V.,Jennings, Elizabeth V.,Gilheany, Declan G.
-
supporting information
p. 14210 - 14214
(2013/11/06)
-
- Transformations of diphenylphosphinothioic acid tertiary amides mediated by directed ortho metallation
-
ortho-Lithiation of N,N-diisopropyl-P,P-diphenylphosphinothioic amide using n-BuLi in the presence of TMEDA in diethyl ether followed by electrophilic trapping is described as an efficient method for the synthesis of ortho-functionalised derivatives in high yields. The structural modification of the phosphinothioic amide includes C-X (X = P, S, Si, Sn, I) and C-C bond forming reactions with a large variety of electrophiles. Additional applications based on functional group transformations are also reported. They include imine formation, desulfurization and Suzuki cross-coupling reactions on selected compounds.
- El Hajjouji, Hajar,Belmonte, Eva,Garcia-Lopez, Jesus,Fernandez, Ignacio,Iglesias, Maria Jose,Roces, Laura,Garcia-Granda, Santiago,El Laghdach, Anas,Lopez Ortiz, Fernando
-
experimental part
p. 5647 - 5658
(2012/08/08)
-
- Studies on the efficient generation of phosphorus-carbon bonds via a rearrangement of PIII esters catalysed by trimethylhalosilanes
-
Halotrimethylsilanes Me3SiX (X = Br, I) catalyse rearrangements of tricoordinate phosphorus esters R′R″P-OR into the corresponding phosphoryl systems R′R″P(O)R. This provides a simple and efficient route to a variety of structures containing phosphorus-carbon bonds, under mild conditions and with good yields. The reaction mechanism was investigated in detail by 31P NMR spectroscopy and independent synthesis of the reaction intermediates. It has been demonstrated that the primary products of this catalytic reaction are halogeno PIII structures R′R″PX and silyl ethers ROSiMe3 and that they subsequently react to give the corresponding phosphorus silyl esters - Me 3SiOPR′R″-and alkyl halides RX. At higher temperatures these intermediates then react to form R′R″P(P)R compounds. This paper also features the surprising observation that when esters Ph 2POR and halotrimethylsilanes Me3SiX (X = Br, I) are used in 2:1 ratio, phosphonium salts Ph2R2P+X - and trimethylsilyl diphenylphosphinate - Ph2P(O) OSiMe3 - are formed as the major products. Experimental evidence indicates that the mechanisms of both reactions are fundamentally different from that of the Michaelis-Arbuzov reaction. Me3SiCl is not reactive and this paper explains why.
- Dabkowski, Wojciech,Ozarek, Alfred,Olejniczak, Sebastian,Cypryk, Marek,Chojnowski, Julian,Michalski, Jan
-
body text
p. 1747 - 1756
(2009/09/25)
-
- Aminodiphenylphosphanes: Isotope-induced chemical shifts 1Δ14/15N(31P), coupling constants 1J(31P,15N), and chemical shifts δ15N and δ31P
-
A series of aminodiphenylphosphanes 1 [Ph2P-N(H)tBu (a), -NEt2 (b), -NiPr2 (c)], 2 [Ph2P-NHPh (a), -NH-2-pyridine (b), -NH-3-pyridine (c), -NH-4-pyridine (d), NH-pyrimidine (e), NH-2,6-Me2-C6/su
- Contreras, Rosalinda,Grevy, Jean Michel,Garcia-Hernandez, Zureima,Goeizado-Rodriguez, Marisol,Wrackmeyer, Bernd
-
p. 542 - 550
(2007/10/03)
-
- The 'one-pot' syntheses of α,α′-diphosphino-substituted imines: A unique reaction of bulky bis(dialkylamino)chlorophosphines
-
The reaction between various bis(dialkylamino)chlorophosphines and N-isopropyl-substituted lithium amides afforded bis(α,α′-phosphino)imines in a 'one-pot' procedure. These compounds react with sulfur to generate intramolecularly hydrogen-bonded ylide derivatives. The molecular structure of (Pr2iN)2PCH2C(=NBut) CH2P(NPri)2 has been determined by X-ray crystallography.
- Baceiredo,Bertrand,Dyer,Fawcett,Griep-Raming,Guerret,Hanton,Russell,Williamson
-
p. 591 - 596
(2007/10/03)
-
- Rearrangement Reactions of N-Phosphinoyl-O-sulphonylhydroxylamines with Amines under Competitive Conditions. Possible Involvement of Monomeric Metaphosphonimidates and Phosphonamidic Sulphonic Mixed Anhydrides
-
The O-methylsulphonyl-N-phosphinoylhydroxylamines, RPhP(O)NHOMs (R=Ph, Me, Et, Pri), react with an excess of an equimolar mixture of isopropylamine and t-butylamine to give the rearrangement products RP(O)(NHPh)(NHPri) and RP(O)(NHPh
- Harger, Martin J. P.,Smith, Adrian
-
p. 2507 - 2511
(2007/10/02)
-