23897-19-0Relevant articles and documents
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.
Phosphine-catalysed reductive coupling of dihalophosphanes
Hering-Junghans, Christian,Schumann, André,Siewert, Jan-Erik
supporting information, p. 15111 - 15117 (2021/11/12)
Classically tetraaryl diphosphanes have been synthesized through Wurtz-type reductive coupling of halophosphanes R2PX or more recently, through the dehydrocoupling of phosphines R2PH. Catalytic variants of the dehydrocoupling reactio
Bismuth Amides Mediate Facile and Highly Selective Pn–Pn Radical-Coupling Reactions (Pn=N, P, As)
Oberdorf, Kai,Hanft, Anna,Ramler, Jacqueline,Krummenacher, Ivo,Bickelhaupt, F. Matthias,Poater, Jordi,Lichtenberg, Crispin
supporting information, p. 6441 - 6445 (2021/02/01)
The controlled release of well-defined radical species under mild conditions for subsequent use in selective reactions is an important and challenging task in synthetic chemistry. We show here that simple bismuth amide species [Bi(NAr2)3] readily release aminyl radicals [NAr2]. at ambient temperature in solution. These reactions yield the corresponding hydrazines, Ar2N?NAr2, as a result of highly selective N?N coupling. The exploitation of facile homolytic Bi?Pn bond cleavage for Pn?Pn bond formation was extended to higher homologues of the pnictogens (Pn=N–As): homoleptic bismuth amides mediate the highly selective dehydrocoupling of HPnR2 to give R2Pn?PnR2. Analyses by NMR and EPR spectroscopy, single-crystal X-ray diffraction, and DFT calculations reveal low Bi?N homolytic bond-dissociation energies, suggest radical coupling in the coordination sphere of bismuth, and reveal electronic and steric parameters as effective tools to control these reactions.
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.
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.
Convenient synthetic method of functional phosphines under photochemical conditions
Yasui, Shinro,Ando, Taro,Ozaki, Masashi,Ogawa, Yuya,Shioji, Kosei
, p. 481 - 483 (2018/04/24)
Steady-state photolysis of triarylphosphines, Ar3P, under an argon atmosphere in a solvent with the structure CH3X (X = CN, COOC2H5, COCH3) afforded an adduct with the solvent molecule, Ar2PCH2X, in significant amount. This photoreaction is acknowledged as a convenient method to prepare functional phosphines.
Selective dehydrocoupling of phosphines by lithium chloride carbenoids
Molitor, Sebastian,Becker, Julia,Gessner, Viktoria H.
supporting information, p. 15517 - 15520 (2014/12/12)
The development of a simple, transition-metal-free approach for the formation of phosphorus-phosphorus bonds through dehydrocoupling of phosphines is presented. The reaction is mediated by electronically stabilized lithium chloride carbenoids and affords a variety of different diphosphines under mild reaction conditions. The developed protocol is simple and highly efficient and allows the isolation of novel functionalized diphosphines in high yields.
Exploration of tin-catalyzed phosphine dehydrocoupling: Catalyst effects and observation of tin-catalyzed hydrophosphination
Erickson, Karla A.,Dixon, Lily S.H.,Wright, Dominic S.,Waterman, Rory
supporting information, p. 141 - 145 (2015/01/09)
The phosphine substrate scope in dehydrocoupling reactions catalyzed by Cp?2SnCl2 (Cp? = pentamethylcyclopentadienyl, 1) have been explored. Catalyst variants R2SnX2 (R = Cp?, Ph; X = Cl, Me, Ph) were also tested, which revealed that activity is dependent on the Cp? ligands as well as more electron withdrawing X ligands. Steric factors at the phosphine substrate are also important. Compound 1 was found to be a catalyst for hydrophosphination of styrene, 2,3-dimethylbutadiene, and diphenylacetylene with phenylphosphine, which is the first example of a p-block catalyst for hydrophosphination.
Monomere Phosphinoborane: Synthese eines Tetraalkylphosphinoborans und seine Umwandlung unter Retro- und Re-hydroborierung zu einem dimeren Phosphinoboran sowie Synthese eines Triphosphinoborans
Karsch, Hans Heinz,Hanika, Gerhard,Huber, Brigitte,Riede, Juergen,Mueller, Gerhard
, p. C25 - C29 (2007/10/02)
The first monomeric tetraalkylphosphinoboranetBu2B=PtBu2 was synthesized from tBu2BBr and LiPtBu2.It decomposes above -20 deg C via double retro-hydroboration and elimination of isobutene, undergoes subsequent re-hydroboration and dimerisation to give stable bis(phosphinoborane)iBu(H)PtBu2>2, whose molecular structure was determined by X-ray diffraction.It containes planar, almost square (BP)2 four-membered ring.The B-P distances are 2.004(4)/2.022(4) Angstroem.The first monomeric triphosphinoborane Me2PB(PMes2)2, was synthesized similarly.All compounds have been characterized by NMR spectroscopy.
