26437-49-0Relevant articles and documents
Efficient One-Pot Synthesis of Mono- and Bis[di(2-pyridyl)phosphine Oxides] from Tris(2-pyridyl)phosphine
Malysheva, Svetlana F.,Gusarova, Nina K.,Belogorlova, Nataliya A.,Sutyrina, Anastasiya O.,Litvintsev, Yuriy I.,Albanov, Alexander I.,Sterkhova, Irina V.,Artem'ev, Alexander V.
, p. 2451 - 2454 (2016/10/24)
An efficient one-pot access to di(2-pyridyl)phosphine oxides Py2P(R)=O and bis[di(2-pyridyl)phosphine oxides] Py2P(O)-Z-P(O)Py has been developed based on the reaction of available tris(2-pyridyl)phosphine with various organic halides, followed by treatment of the resulting phosphonium salts with alkali in situ. The isolated yields of the phosphine oxides were in the range 40-96%.
2-Pyridyl-phosphine and -diphosphine complexes of nickel(0), their reactivity (including aqueous solution chemistry), and some related, incidental methylphosphonium iodides
Le Page, Matthew D.,Patrick, Brian O.,Rettig, Steven J.,James, Brian R.
, p. 276 - 288 (2015/06/02)
The chemistry of Ni0-dicarbonyl(pyridylphosphine) complexes of the type Ni(CO)2L2, where L is either P-bonded PPh3-npyn (n = 1-3, py = 2-pyridyl; abbreviated PNx, x = 1-3, species 1a-c), or L2 is (P-P)-chelated py2P(CH2)2Ppy2 or, is further developed from earlier studies by our group [the P-P ligands are abbreviated, respectively, as d(py)pe and d(py)pcp]. The complexes are synthesized from C6H6 solutions of Ni(CO)2(PPh3)2, and the Ni(CO)2(PPh3)(PNx) intermediates (1a-c) are detected; Ni(CO)2[d(py)pcp] (2b) is shown by X-ray analysis to have a distorted tetrahedral structure; and the NiII species [Ni2(CO)4(μ-PN2)2]Cl4 is isolated from a light-induced reaction in CDCl3 solution. Complex 2b dissolves in water at ambient conditions via a net double protonation of pyridyl N-atoms, the {Ni(CO)2[2H-d(py)pcp]}2+ being isolated as the bis(triflate) salt; the dication decomposes in minutes with formation of [Ni(H2O)6]2+, CO, the phosphine dioxide, and deprotonated d(py)pcp. Some twenty-two Ni0 complexes, exemplified by Ni(P-P)2, Ni(PNx)2(P-P), Ni(PNx)4, and related PPh3- and Ph2P(CH2)2PPh2 (dppe)-containing species, are synthesized from Ni(1,5-COD)2 and their reactivity studied; for example, oxidative addition of MeI generates trans-Ni(Me)(I)(PN3)2 and trans-Ni(Me)(I)(P-P)2 but, with non-pyridyl containing reactants such as Ni(PPh3)4 and Ni(dppe)2, only (monomethyl)phosphonium iodides are formed. Such iodides, and the bis(methyl) analogues [(CH3)2(diphosphine)]I2, are then studied for clarification of some observed Ni chemistry. The NMR trends (a)-(d) are noted within the series of Ni0 complexes, and are rationalized: (a) the 2JPP values in 1a-c, and the separation between the two doublets, parallel the number of N-atoms present; (b) the 31P{1H} signals in the Ni(PNx)4 and Ni(PNx)2(P-P) complexes shift downfield in the order PN1 2 3 within linear dependences; (c) the 2JPP values for the Ni(PR3)2(P-P) complexes (R = Ph and PNx) decrease in the order R = Ph > PN1 > PN2 > PN3; (d) and the separation between the two 31P{1H} triplets of the Ni(PNx)2(P-P) complexes generally depends on the relative numbers of phenyl and pyridyl groups.
Reaction of Tri(2-pyridyl)phosphine with Electron-Deficient Alkynes in Water: Stereoselective Synthesis of Functionalized Pyridylvinylphosphine Oxides
Arbuzova, Svetlana N.,Gusarova, Nina K.,Glotova, Tatyana E.,Ushakov, Igor A.,Verkhoturova, Svetlana I.,Korocheva, Anastasiya O.,Trofimov, Boris A.
, p. 639 - 643 (2015/10/05)
The reaction of tri(2-pyridyl)phosphine with electron-deficient alkynes in water proceeds under mild conditions (40-45 C, without catalyst, 4-5 h) with liberation of pyridine to give (E)-pyridylvinylphosphine oxides in 45-56 % yields, the only exception being the reaction with cyanophenylacetylene, which affords the corresponding vinylphosphine oxide of Z-configuration in 40 % yield. The reaction is likely triggered by the zwitterion, the adduct of tri(2-pyridyl)phosphine to the electrophilic acetylenes, the carbanionic center of which is then neutralized by a proton from water. The intermediate phosphonium hydroxide finally decomposes to the product.
Reaction of tri(2-pyridyl)phosphine with electron-deficient alkynes in water: Stereoselective synthesis of functionalized pyridylvinylphosphine oxides
Arbuzova, Svetlana N.,Gusarova, Nina K.,Glotova, Tatyana E.,Ushakov, Igor A.,Verkhoturova, Svetlana I.,Korocheva, Anastasiya O.,Trofimov, Boris A.
, p. 639 - 643 (2014/02/14)
The reaction of tri(2-pyridyl)phosphine with electron-deficient alkynes in water proceeds under mild conditions (40-45 °C, without catalyst, 4-5 h) with liberation of pyridine to give (E)-pyridylvinylphosphine oxides in 45-56 % yields, the only exception being the reaction with cyanophenylacetylene, which affords the corresponding vinylphosphine oxide of Z-configuration in 40 % yield. The reaction is likely triggered by the zwitterion, the adduct of tri(2-pyridyl)phosphine to the electrophilic acetylenes, the carbanionic center of which is then neutralized by a proton from water. The intermediate phosphonium hydroxide finally decomposes to the product. The one-pot stereoselective synthesis of functionalized pyridylvinylphosphine oxides has been elaborated through the straightforward reaction of tri(2-pyridyl)phosphine with electron-deficient alkynes in water. The reaction is accompanied by liberation of the pyridine molecule. Copyright
Expedient one-pot organometallics-free synthesis of tris(2-pyridyl) phosphine from 2-bromopyridine and elemental phosphorus
Trofimov, Boris A.,Artem'Ev, Alexander V.,Malysheva, Svetlana F.,Gusarova, Nina K.,Belogorlova, Nataliya A.,Korocheva, Anastasiya O.,Gatilov, Yuriy V.,Mamatyuk, Victor I.
supporting information; experimental part, p. 2424 - 2427 (2012/06/01)
2-Bromopyridine reacts with elemental phosphorus (red or white) in a superbasic KOH/DMSO(H2O) suspension at 100 °C (for red phosphorus) and 75 °C (for white phosphorus) over 3 h to afford tris(2-pyridyl)phosphine in a 62% yield (from red phosphorus) and a 50% yield (from white phosphorus). Under microwave assistance, the reaction with red phosphorus takes just 20 min to produce tris(2-pyridyl)phosphine in 53% yield. A hitherto unknown complex, [Pd(PPy3)2Cl 2]·CH2Cl2, synthesized from tris(2-pyridyl)phosphine and PdCl2, has the cis-configuration; this is unusual for bis(phosphino)palladium dichloride complexes.
