68357-98-2Relevant academic research and scientific papers
Photocatalytic Arylation of P4 and PH3: Reaction Development Through Mechanistic Insight
Cammarata, Jose,Gschwind, Ruth M.,Lennert, Ulrich,Rothfelder, Robin,Scott, Daniel J.,Streitferdt, Verena,Wolf, Robert,Zeitler, Kirsten
supporting information, p. 24650 - 24658 (2021/10/14)
Detailed 31P{1H} NMR spectroscopic investigations provide deeper insight into the complex, multi-step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P4). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non-innocent behavior of the commonly employed terminal reductant Et3N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy)2][PF6] (dtbbpy=4,4′-di-tert-butyl-2,2′-bipyridine) and 3DPAFIPN. Inspired by the observation of PH3 as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.
The formation of mesitylphosphine and dimesitylphosphine in the reaction of organonickel σ-complex [NiBr(Mes)(bpy)] (Mes = 2,4,6-trimethylphenyl, bpy = 2,2′-bipyridine) with phosphine PH3
Gafurov, Zufar N.,Sakhapov, Il’yas F.,Kagilev, Alexey A.,Kantyukov, Artyom O.,Khayarov, Khasan R.,Sinyashin, Oleg G.,Yakhvarov, Dmitry G.
, p. 726 - 729 (2020/04/29)
The reactivity of the previously reported organonickel σ-complex [NiBr(Mes)(bpy)], where Mes = 2,4,6-trimethylphenyl, bpy = 2,2′-bipyridine, toward phosphine PH3 was investigated. The reaction leads to primary mesitylphosphine MesPH2
Multinuclear Cu(I) Clusters Featuring a New Triply Bridging Coordination Mode of Phosphaamidinate Ligands
Rathnayaka, Suresh C.,Lindeman, Sergey V.,Mankad, Neal P.
, p. 9439 - 9445 (2018/08/17)
Phosphabenzamidine [mes-NH-C(Ph)=P-mes) (1) and phosphaformamidine (mes-NH-CH=P-mes) (4) ligands have been synthesized and characterized. The conjugate bases of 1 and 4 coordinate by each bridging three Cu(I) ions, forming hexa- and tetranuclear clusters Cu6[mes-N=C(Ph)-P-mes]3Cl4Li(THF)2 (3) and Cu4[mes-N=CH-P-mes]4 (5), respectively. Both clusters have been fully characterized using 1H NMR, 31P NMR, and X-ray crystallography. Complexes 3 and 5 exhibit a previously unknown coordination mode of phosphaamidinates, which are far less studied than their well-known amidinate counterparts.
2,6-diphospha-s-indacene-1,3,5,7(2H,6H)-tetraone: A phosphorus analogue of aromatic diimides with the minimal core exhibiting high electron-accepting ability
Takeda, Youhei,Nishida, Takuya,Minakata, Satoshi
supporting information, p. 10266 - 10270 (2014/08/18)
Phosphorus analogues of pyrromellitic diimides (PyDIs), which represent a family of privileged electron-accepting organic compounds, have been successfully synthesized as novel electron-accepting π-conjugated molecules. Investigation into their physicochemical properties uncovered their prominent electron-accepting abilities over the corresponding PyDI. Furthermore, theoretical studies revealed the significant contribution of σ*-π* hyperconjugation in stabilizing the LUMO+1.
Phosphino[tris(trimethylsilyl)methyl]boranes and 2,4- bis[tris(trimethylsilyl)methyl]-1,3,2,4-diphosphadiboretanes [1]
Jetzfellner,Noeth,Paine
, p. 548 - 556 (2008/10/09)
The reaction of tris(trimethylsilyl)methylboron dihalides (Me 3Si)3CBX2 (X = Cl, F) with the lithium phosphides LiPHtBu and LiPHmes leads to the phosphinoboranes (Me 3Si)3CBX-(PHR), (Me3Si)3CB(PHR) 2 or the 1,3,2,4-diphosphadiboretanes [(Me3Si) 3CB(PR)]2, depending on the ratio of the reagents, the reaction temperature and concentration. High dilution and low temperatures are required for the synthesis of (Me3Si)3CB(Hal)PHR (1-3) in order to prevent the formation of (Me3Si)3CB(PHR) 2 (4 and 5). The latter compounds are best prepared in a two step phosphination from (Me3Si)3CBHal2 and LiPHR. At higher temperatures the four-membered 1,3,2,4-diphosphadiboretanes [(Me 3Si)3CB(PR)]2 6 and 7 are the most stable compounds. On the other hand, compounds of type (Me3Si) 3CB(Hal)PR2, 8 and 9, are thermally more stable than the monophosphinoboranes 1-3. Phosphinoboranes of type (Me3Si) 3CB(PR2)2 (R = tBu, mes) could not be prepared. NMR and mass spectral data are in accord with the monomeric nature of compounds 1 to 9.
Amino-functionalised diarylphosphide complexes of the alkali metals and lanthanum
Izod, Keith,Liddle, Stephen T.,Clegg, William,Harrington, Ross W.
, p. 3431 - 3437 (2007/10/03)
The secondary phosphines Ar(C6H4-2-CH 2NMe2)PH [Ar = mes (3), Tripp (4)] may be isolated in good yields from reactions between Li(C6H4-2-CH 2NMe2) and the respective dichlorophosphine, followed by reduction with LiAlH4 [mes = 2,4,6-Me3C6H 2, Tripp = 2,4,6-Pri3C6H 2]. Metalation of either 3 or 4 with BunLi gives the corresponding lithium compound; the lithium derivative of 3 was isolated as the separated ion pair complex [Li(12-crown-4)2][(mes)(C 6H4-2-CH2NMe2)P]·THF (5). The lithium complexes Ar(C6H4-2-CH2NMe 2)PLi undergo metathesis reactions with either NaOBut or KOBut to give the heavier alkali metal phosphides {Ar(C 6H4-2-CH2NMe2)P}M·1/2OEt 2 [Ar = mes, M = Na (8), K (9); Ar = Tripp, M = K (10)]. Metathesis reactions between 9 and LaI3(THF)4 give only intractable products; in contrast, a metathesis reaction between 10 and LaI 3(THF)4 yields the heteroleptic complex {(Tripp)(C 6H4-2-CH2NMe2)P}2LaI (11). Compound 11 reacts cleanly with K{N(SiMe3)2} to give {(Tripp)(C6H4-2-CH2NMe2)P} 2La{N(SiMe3)2} (14). Compounds 3-5, 8-11 and 14 have been characterised by multi-element NMR spectroscopy; in addition, compounds 5, 11 and 14 have been studied by X-ray crystallography. The Royal Society of Chemistry 2006.
