1732-66-7Relevant academic research and scientific papers
Alkyne 1,1-Hydroboration to a Reactive Frustrated P/B-H Lewis Pair
?koch, Karel,Daniliuc, Constantin G.,Kehr, Gerald,Erker, Gerhard
, p. 6757 - 6763 (2021)
The Mes2P-C≡C-SiMe3 alkyne reacts with the borane H2B-Fmes by means of a rare 1,1-hydroboration reaction to give an unsaturated C2-bridged frustrated P/B-H Lewis pair. Most of its reactions are determined by the presence of the B-H functionality at the FLP function and the activated connecting carbon-carbon double bond. It reduces carbon monoxide to the formyl stage. With nitriles it reacts in an extraordinary way: it undergoes a reaction sequence that eventually results in the formation of a P-substituted dihydro-1,2-azaborole derivative. Several similar examples were found. In one case a P-ylide was isolated that was related to an intermediate of the reaction sequence. It subsequently opened in an alternative way to give an alkenyl borane product.
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)
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
Reactions of activated organonickel σ-complexes with elemental (white) phosphorus
Yakhvarov,Kvashennikova,Sinyashin
, (2013)
The reactivity of organonickel σ-complexes of the type [NiBr(Ar)(bpy)] (Ar is 2,4,6-tri-methylphenyl (Mes) or 2,4,6-triisopropylphenyl (Tipp); bpy is 2,2′-bipyridine) toward elemental (white) phosphorus was studied. For the reaction to occur, the complexe
9-BBN and chloride catalyzed reduction of chlorophosphines to phosphines and diphosphines
Andrews, Ryan J.,Elser, Iris,Stephan, Douglas W.
supporting information, p. 1740 - 1743 (2022/02/17)
The commercially available Lewis acid, 9-BBN and Lewis basic [Et4N]Cl are used as catalysts for the reduction of chlorophosphines R2PCl in the presence of phenylsilane. Aryl-chlorophosphines afford primarily diphosphines (P2R4) while secondary phosphines predominate for alkyl-substituted precursors. Use of the combined catalysts leads to reduced reaction time and temperature, providing a rapid, scalable, and facile protocol for the preparation of diphosphines or secondary phosphines.
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.
Insertion reaction of chalcogens into an al-p bond
Mizuhata, Yoshiyuki,Tokitoh, Norihiro,Yanagisawa, Tatsuya
, (2020/07/21)
We examined the reactions of a phosphanylalumane () with chalcogen sources as a part of our investigation of the reactivity of the Al P bonds. In the case of sulfur source, two S atoms were inserted into the Al P bond to afford an [Al S P 5] heterocycle. Structural analysis and theoretical calculations revealed a charge-separated structure between the [Al] and [S2P] moieties of the [Al S P 5] 4-membered ring, which is different from the [B S P 5] ring having concrete B S o-bonds in the 4-membered ring.
Palladium-Based Hydroamination Catalysts Employing Sterically Demanding 3-Iminophosphines: Branched Kinetic Products by Prevention of Allylamine Isomerization
Thakuri, Rajendr S.,Schmidt, Joseph A. R.
, p. 1917 - 1927 (2019/05/21)
A new allylpalladium triflate catalyst with a dimesitylphosphine moiety was synthesized, isolated, and characterized. The greatly increased steric bulk on the phosphine of this palladium catalyst inhibited product isomerization, which is often observed after hydroamination of terminal allenes with secondary amines. The considerably reduced rate of isomerization facilitated the isolation of many previously unknown branched allylamines, products that were inaccessible when using other, more active 3-iminophosphine palladium catalysts.
A new method to prepare functional phosphines through steady-state photolysis of triarylphosphines
Yasui, Shinro,Ando, Taro,Ozaki, Masashi,Ogawa, Yuya,Shioji, Kosei
, (2019/01/04)
The steady-state photolysis of triarylphosphine, Ar3P, was carried out using a xenon lamp or a high-pressure mercury lamp under an argon atmosphere in a solvent containing a functional group, CH3X. Gas chromatograph-mass spectroscopic analysis on the photolysis showed that a phosphine to which the functional group from the solvent is incorporated, Ar2PCH2X, was formed in a moderate yield, along with tetraaryldiphosphine, Ar2PPAr2. The product, Ar2PCH2CN, from the photolysis in acetonitrile (X=CN) was isolated by column chromatography. In the photolysis in other solvents tried here (ethyl acetate, acetone, 2-butanone, and 3,3-dimethyl-2-butanone), Ar2PCH2X formed in the reaction mixture was so labile on a silica-gel column that it was treated with S8 powder to convert to the corresponding phosphine sulfide, Ar2P(=S)CH2X. The resulting phosphine sulfide was isolated by column chromatography. The isolated products in these reactions, Ar2PCH2CN and Ar2P(=S)CH2X, were characterized by 1H, 13C, and 31P NMR spectroscopy, IR spectroscopy, and elemental analysis or high-resolution mass spectroscopy. The formation of Ar2PCH2X as well as Ar2PPAr2 is explained by homolytic cleavage of a P-C bond of Ar3P in the photoexcited state. This reactivity of Ar3P in the photoexcited state is in sharp contrast to that exerted under aerobic conditions, where Ar3P in the photoexcited state donates readily an electron to oxygen producing the radical cation, Ar3P·+. This photoreaction, which affords a functional phosphine, Ar2PCH2X, in one-pot with generating very small amounts of unidentified side products, has potential for use in preparing functional phosphines.
Reactions of Low-Coordinate Cobalt(0)-N-Heterocyclic Carbene Complexes with Primary Aryl Phosphines
Wang, Dongyang,Chen, Qi,Leng, Xuebing,Deng, Liang
supporting information, p. 15600 - 15609 (2019/01/04)
Aiming to get knowledge on the reactivity of low-coordinate cobalt(0) species toward primary phosphines, the reactions of [(IPr)Co(vtms)2] and [(ICy)2Co(vtms)] (IPr = 1,3-bis(2′,6′-diisopropylphenyl)imidazol-2-ylidene, ICy = 1,3-dicyclohexylimidazol-2-ylidene, and vtms = vinyltrimethylsilane) with several primary aryl phosphines have been examined. The reactions of [(IPr)Co(vtms)2] and [(ICy)2Co(vtms)] with H2PDmp (Dmp = 2,6-dimesitylphenyl) at 80 °C furnish the diamagnetic cobalt(I) phosphido complexes [(NHC)Co(PHDmp)] (NHC = IPr, 1; ICy, 2) that feature the Co-(η6-mesityl) interaction. Complex 1 can coordinate CO to generate the terminal phosphido complex [(IPr)Co(CO)3(PHDmp)] (3) and can be oxidized by [Cp2Fe][BArF4] to yield the cobalt(II) phosphido complex [(IPr)Co(PHDmp)][BArF4] (4, BArF4 = tetrakis(3,5-di(trifluoromethyl)phenyl)borate). For the reactions with sterically less-hindered primary phosphines, [(IPr)Co(vtms)2] is inert toward H2PC6H2-2,4,6-Me3 (H2PMes) at room temperature, whereas [(ICy)2Co(vtms)] can react with H2PMes at room temperature to produce the cobalt(II) phosphido alkyl complex trans-[(ICy)2Co(CH2CH2SiMe3)(PHMes)] (5). At 80 °C, the cobalt(0) alkene complexes [(IPr)Co(vtms)2] and [(ICy)2Co(vtms)] and also the cobalt phosphido complexes, 1, 2, and 5 can serve as precatalysts for the dehydrocoupling reaction of H2PMes to afford MesHPPHMes. NHC-Co(I)-phosphido species are proposed as the in-cycle intermediates for these cobalt-catalyzed dehydrocoupling reactions.
