- Co-ordination Kinetics of Some Aliphatic Amines towards the Photogenerated Transient 'CoH3'
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Time-resolved adsorption spectra were observed after nitrogen-laser flash photolysis of toluene solutions of in the presence of some aliphatic amines, and second-order rate constants were evaluated for co-ordination of the amines to the co-ordinatively unsaturated transient 'CoHL3' photogenerated.The steric bulk of substituents on the amine nitrogens is a dominant factor in the magnitude of the constants.The CoHL3(amine) adducts were also formed upon continuoes photolysis with a high-pressure mercury lamp, and found to be stable at temperatures lower than -40 deg C, on the basis of their (31)P n.m.r. and visible absorption spectra.
- Onishi, Masayoshi,Takaki, Isato,Hiraki, Katsuma,Oishi, Shigero
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Read Online
- Silver-Catalyzed Regioselective Phosphorylation of para-Quinone Methides with P(III)-Nucleophiles
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A simple and efficient method for the silver-catalyzed regioselective phosphorylation of para-quinone methides (p-QMs) with P(III)-nucleophiles (P(OR)3, ArP(OR)2, Ar2P-OR) has been established via Michaelis-Arbuzov-type reaction. A broad range of P(III)-nucleophiles and para-quinone methides are well tolerated under the mild conditions, giving the expected diarylmethyl-substituted organophosphorus compounds with good to excellent yields. Moreover, a series of corresponding enantiomers can be obtained by employing dialkyl arylphosphonite (ArP(OR)2) as substrates. The control experiments and 31P NMR tracking experiments were also performed to gain insights for the plausible reaction mechanism. This protocol may have significant implications for the formation of C(sp3)-P bonds in Michaelis-Arbuzov-type reactions.
- Liu, Yu,Tang, Ke-Wen,Wong, Wai-Yeung,Xie, Jun,Xiong, Biquan,Xu, Shipan,Xu, Weifeng
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p. 14983 - 15003
(2021/11/12)
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- Scalable Enantiomeric Separation of Dialkyl-Arylphosphine Oxides Based on Host–Guest Complexation with TADDOL-Derivatives, and their Recovery
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Several dialkyl-arylphosphine oxides were prepared, and the enantioseparation of the corresponding racemates was elaborated with host–guest complexation using TADDOL-derivatives. The crystallization conditions were optimized and two separate crystallization methods, one in organic solvent, and the other in water, were found to yield five examples of phosphine oxides with enantiomeric excess values higher than 94 %. A gram scale resolution was performed, and both enantiomers of the methyl-phenyl-propyl-phosphine oxide were separated with (R,R)- or (S,S)-spiro-TADDOL. The intermolecular interactions responsible for the enantiomeric recognition between the chiral host and guest molecules were investigated by single-crystal X-ray diffractional structural determinations. The similarities in the structural patterns of a few diastereomeric crystals were checked by powder X-ray diffraction, as well. Organic solvent nanofiltration (OSN) was used as a scalable technique for the decomposition of the corresponding phosphine oxide–spiro-TADDOL molecular complexes, and for the recovery of the phosphine oxide enantiomers and resolving agents.
- Bagi, Péter,Fogassy, Elemér,Herbay, Réka,Holczbauer, Tamás,Keglevich, Gy?rgy,Mátrav?lgyi, Béla,Madarász, János,Székely, Gy?rgy,Varga, Bence
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supporting information
(2020/03/23)
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- New preparation method of first-class phenyl phosphine oxide initiator
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The invention provides a new preparation method of a first-class phenyl phosphine oxide initiator. The method comprises the steps that (1) benzene and aluminum trichloride are added into a reaction vessel and stirred uniformly, then phosphorus trichloride is added, the temperature is slowly increased, and after a complete reaction, the temperature is reduced to room temperature; (2) a reaction mixture obtained in the step (1) is slowly added dropwise into a solvent containing a decomplexing agent, and the temperature is controlled for decomplexing; (3) a decomplexing product obtained in the step (2) is filtered to separate solids, and filtrate is subjected to pressure reduction distillation to obtain phenyl dialkoxy phosphine or diphenyl alkoxy phosphine; (4) a product obtained in the step(3) is dissolved in a benzene or methylbenzene solvent, and a trichloromethyl acetyl compound is added dropwise for a reaction; and (5) a solution obtained after the complete reaction in the step (4)is subjected to low-pressure desolvation, and light-yellow liquid or solid, namely the phenyl phosphine oxide initiator, is obtained through crystallization, suction filtering and drying. The methodhas the advantages that raw materials are easy to obtain, cost is low, operation is easy to perform, and mass production can be realized.
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Paragraph 0049-0051
(2020/03/05)
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- Efficient Synthesis of Phosphonamidates through One-Pot Sequential Reactions of Phosphonites with Iodine and Amines
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A one-pot sequential strategy to construct phosphonamidates has been developed by generating phosphonites in situ from arylmagnesium bromides and triethyl phosphite followed by treatment with iodine and amines. A variety of phosphonamidates were obtained with good to excellent yields at room temperature from easily available materials.
- Chen, Xunwei,Luo, Wenjun,Wang, Yanlin,Li, Zikang,Ma, Xiaorui,Peng, Ai-Yun
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p. 14474 - 14480
(2020/10/06)
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- Preparation of O-Protected Cyanohydrins by Aerobic Oxidation of α-Substituted Malononitriles in the Presence of Diarylphosphine Oxides
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A mild, reagent-cyanide-free, and efficient synthesis of O-phosphinoyl-protected cyanohydrins from readily available α-substituted malononitriles was realized using diarylphosphine oxides in the presence of O2. Mechanistic studies indicated that in addition to the initial aerobic oxidation of the malononitrile derivative notable features of this process include the formation of a tetrahedral intermediate and a subsequent intramolecular rearrangement. The phosphinoyl-protecting group can be removed by alcoholysis or by reduction with DIBAL-H.
- Zhang, Dapeng,Lian, Mingming,Liu, Jia,Tang, Shukun,Liu, Guangzhi,Ma, Cunfei,Meng, Qingwei,Peng, Haisheng,Zhu, Daling
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supporting information
p. 2597 - 2601
(2019/04/17)
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- Aryl(dimethylaminomethyl)phosphinic Acid Esters: Syntheses, Structures, and Reactions with Halogen Hydrogen Acids, Tin Halides, and Trimethyl Halosilanes
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This paper reports the synthesis of the aryl(iodomethyl)phosphinic acid ethyl esters, Ar(ICH2)P(O)OEt (Ar = Ph, Ar = mesityl), which, via dimethyamination, are converted to the corresponding aryl(dimethylaminomethyl)phosphinic acid ethyl esters, Ar(Me2NCH2)P(O)OEt (Ar = Ph, Ar = mesityl). Upon reaction with hydrogen chloride, compound Me2NCH2(Ph)P(O)OEt forms its hydrochloride salt as a crystalline material. Depending on the reaction conditions, treatment of Me2NCH2(Ph)P(O)OEt with SnCl2 gave either [Me2HNCH2(Ph)P(O)OEt][SnCl3] or the mixed-valent dinuclear tin salt [{Me2HNCH2(Ph)P(O)O}4SnCl2][SnCl3]2, as its dichloromethane solvate. The reaction of Me2NCH2(Mes)P(O)OEt with SiMe3I gives the diorgano bis(trimethylsiloxy)phosphinium iodide [Me2NCH2(Mes)P(OSiMe3)2]I, as its toluene solvate. In solution, it is involved in an equilibrium with Me2NCH2(Mes)P(O)OSiMe3 and SiMe3I. From the hydrolysis of [Me2NCH2(Mes)P(OSiMe3)2]I, the hydrogen iodide derivative [Me2HNCH2(Mes)P(O)OH]I was obtained as three different solvates. [Me2NCH2(Mes)P(OSiMe3)2]I reacted with SnF2 to give a product mixture from which the mixed-valent tin compound [{SnII2Me2NCH2(Mes)P(O)2}4SnIVF2]I2, was isolated. The compounds were characterized by NMR and IR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analysis.
- Lutter, Michael,Jurkschat, Klaus
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p. 3481 - 3490
(2018/08/21)
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- Preparation method for catalytically compounding benzyl phosphonate by using basic ionic liquid
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The invention belongs to the technical field of organic synthesis and relates to a preparation method for benzyl phosphonate as a key intermediate of an acyl phosphine oxide type photoinitiator. According to the method, benzene, phosphorus trichloride and alkyl alcohol are taken as main raw materials and are compounded into benzyl phosphonate through two-step reaction. The preparation method is characterized in that a target product is generated through the low-temperature reaction of the dichlorophenyl phosphine and alcohol under the condition of a gemini basic ionic liquid catalyst in the second step reaction, the reaction temperature is controlled within -10 DEG C to 10 DEG C, the dichlorophenyl phosphine is dropwise added and then the mixture reacts for 0.5-7 hours under a stirring condition after the temperature is increased to 30-50 DEG C. The preparation method has the advantages of low cost, simple and convenient after-treatment, high yield, and the like, and is suitable for industrial production.
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Paragraph 0042; 0044; 0045; 0062
(2018/01/12)
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- Identification of the Privileged Position in the Imidazo[1,2-a]pyridine Ring of Phosphonocarboxylates for Development of Rab Geranylgeranyl Transferase (RGGT) Inhibitors
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Members of the Rab GTPase family are master regulators of vesicle trafficking. When disregulated, they are associated with a number of pathological states. The inhibition of RGGT, an enzyme responsible for post-translational geranylgeranylation of Rab GTPases represents one way to control the activity of these proteins. Because the number of molecules modulating RGGT is limited, we combined molecular modeling with biological assays to ascertain how modifications of phosphonocarboxylates, the first reported RGGT inhibitors, rationally improve understanding of their structure-activity relationship. We have identified the privileged position in the core scaffold of the imidazo[1,2-a]pyridine ring, which can be modified without compromising compounds' potency. Thus modified compounds are micromolar inhibitors of Rab11A prenylation, simultaneously being inactive against Rap1A/Rap1B modification, with the ability to inhibit proliferation of the HeLa cancer cell line. These findings were rationalized by molecular docking, which recognized interaction of phosphonic and carboxylic groups as decisive in phosphonocarboxylate localization in the RGGT binding site.
- Ka?mierczak, Aleksandra,Kusy, Damian,Niinivehmas, Sanna P.,Gmach, Joanna,Joachimiak, ?ukasz,Pentik?inen, Olli T.,Gendaszewska-Darmach, Edyta,B?azewska, Katarzyna M.
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supporting information
p. 8781 - 8800
(2017/11/15)
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- McKenna reaction - Which oxygen attacks bromotrimethylsilane?
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The first experimental proof of the course of silylation in the McKenna reaction, one of the most widely used reactions for the synthesis of organophosphorus acids, is presented. The reaction (in acetonitrile) proceeds via an attack of the terminal oxygen from the dialkyl phosphonate on the silicon atom in bromotrimethylsilane. Isotopically enriched diethyl phenylphosphonates (Pi - 17O or Pi - 18O) were used as the model compounds. The location of the isotopic tracers was detected using 31P and 17O NMR spectroscopy.
- Blazewska, Katarzyna M.
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p. 408 - 412
(2014/01/17)
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- Revisited synthesis of aryl-H-phosphinates
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A systematic study of the reaction conditions for the preparation of pure aryl-H-phosphinate esters, originally developed by Sander and optimized by Petnehazy, is reported. The influence of the reaction concentration has been investigated for the formation of phosphonite intermediates via direct addition of triethyl phosphite to the appropriate Grignard reagent. Subsequent hydrolysis of the phosphonites under acidic conditions gives various aryl-H-phosphinates in high yields and purities. Georg Thieme Verlag Stuttgart, New York.
- Volle, Jean-Noel,Filippini, Damien,Midrier, Camille,Sobecki, Michal,Drag, Marcin,Virieux, David,Pirat, Jean-Luc
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experimental part
p. 2490 - 2494
(2011/09/20)
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- Polyfluoroalloxy phosphonic and phosphinic acid derivatives: I. 1-Hydroxy-2,2,2-trichloroethylphosphinates
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Polyfluoroalkyl esters of 1-hydroxy-2,2,2-trichloroethylphosphonic and aryl(alkyl-)phosphinic acids exhibited antienzyme activity towards esterases of animal and microbial origin. A good correlation is observed between high antiesterase activity of the target compounds and their physicochemical parameters, characterizing their structure.
- Krutikova,Krutikov,Erkin
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experimental part
p. 428 - 433
(2010/08/04)
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- Synthesis and structure of [η4- tetrakis(arylethoxyphosphoryl)cyclobutadiene]-(η5- cyclopentadienyl)cobalt(I) complexes
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[η4-Tetrakis(arylethoxyphosphoryl)cyclobutadiene] (η5-cyclopentadienyl)cobalt(I) complexes were synthesized by reaction of bis(arylethoxyphosphoryl)acetylenes with CpCo(CO)2 and several diastereomers were isolated. Whole molecular structure of the tetraphosphorylcyclobutadiene complex was significantly affected by relative configuration of the phosphoryl groups.
- Sasaki, Shigeru,Kato, Kiyotoshi,Tanabe, Yoshihiro,Yoshifuji, Masaaki
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p. 1004 - 1005
(2007/10/03)
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- Convenient one pot synthesis of phosphonites and H-phosphinates
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A convenient and simple one-pot method is described for the synthesis of phosphonites [RP(OEt)2, 1] and H-phosphinates [HP(O)R(OEt), 2] from triethyl phosphite and appropriate Grignard reagents.
- Petnehazy, Imre,Jaszay, Zsuzsa M.,Szabo, Andrea,Everaert, Kinga
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p. 1665 - 1674
(2007/10/03)
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- Intramolecular nucleophilic displacement of halogen by phosphinate and thiophosphinate anions: Relative rates of formation of five- And six-membered rings 1
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Intramolecular nucleophilic substitution transforms the phosphinate anions XCH2CH2(CH2)nCH2(Ph)P(O)O (n = 0, 1; X = Br, Cl) (Et3NH+ salts; CH2Cl2 solution) into cyclic phosphinate esters 14 (n - 0,1); unusually the five-membered ring product (n = 0) is formed only 4.3 (X = Br) or 5.7 (X = Cl) times faster than the six (n = 1). The analogous cyclisation of the thiophosphinate anions ClCH2CH2(CH2)nCH 2(Ph)P(S)CT (n = 0,1) gives the products 16 (n = 0, 1) with the sulfur atom in the ring; the five-membered ring is now formed 30 times faster than the six, still a rather modest rate advantage.
- Chaudhry, Amirah,Hargcr, Martin J. P.,Shuff, Philippa,Thompson, Alison
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p. 1347 - 1352
(2007/10/03)
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- New syntheses of 1-chloroalkylphosphinates
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Different approaches to the synthesis of 1-chloroalkylphosphinates are described. Initially, we tried to extend a reaction described by Kabachnik for the preparation of chloromethylphosphinic acid chlorides [R1(Cl)P(O)CH2Cl] to C-substituted derivatives. We also considered the possibility of synthesizing the title compounds by routes already described for the formation of diethyl 1-chloroalkylphosphonates. Although these methods have allowed us to obtain several of the desired phosphinates, they suffer from limitations that restrict their synthetic applications. Finally, we have developed a more general approach that allows the formation of a wide range of phosphinates. It involves a selective P-C bond formation by reaction of MeMgCl and PhMgCl with phosphonochloridates, which are prepared by P-chlorination of 1-chloroalkylphosphonates.
- Morise, Xavier,Savignac, Philippe,Denis, Jean-Marc
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p. 2179 - 2185
(2007/10/03)
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- C-fluorinated phosphate analogues
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C-fluorinated phosphinic acid derivatives RP(O)(OEt)CF2Br (R = Ph, Me) 2a, b and 1)>2CF2 (R = Ph, R1 = Et, H) 3, 4 have been prepared via a Michaelis-Arbuzov reaction.The signs of the scalar coupling constants in the AMX spin system of (EtO)2P(O)CHFCOOEt (5) formed by the P, F and H of the P-C(H)F unit were determined using spin-tickling techniques.
- Boetzel, Ruth,Haegele, Gerhard
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- Syntheses de phosphobetaines amphiphiles neutres a distances intercharge variables
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Neutral amphiphilic phosphonato- and phosphinatobetaines having different interionic distances are synthesized.Two paths for this synthesis have been studied. 2-(Ethoxy or phenyl) 2-oxo 1,2-oxaphospholanes react with lipophilic tertiary amines at 150 deg C, giving rise to mixtures of phosphobetaines and oxaphospholanate ammonium salts.Lewis acids increase the reaction rate but cannot change the selectivity.The specific production of phosphobetaines is achieved by a three steps sequence: the Arbusov reaction is applied to α,ο-dibromoalcanes and triethylphosphite or phenyldiethylphosphonite, providing ο-bromophosphonates in high yield.Tertiary amines are then condensed, followed by a bromide to hydroxide ions exchange on an anion exchange resin.Phosphobetaines are then specifically formed by thermal elimination of ethanol above the critical micellar concentration.Howewer, when Hoffmann elimination competes with basic hydrolysis of the phenylphosphinic ester groups, acidic hydrolysis is preferred, followed by neutralization with an OH- anion exchange resin.This preparative specific synthesis procedure affords pure, neutral and inorganic salt free zwitterionic compounds for a whole series of homologues.The physical properties of such compounds are believed to be designed upon the chice of the substituents (alkyl chain length, interionic methylene number, ethoxy or phenyl substituent at the phosphorous atom).
- Germanaud, Laurent,Brunel, Sylvian,Chevalier, Yves,Le Perchec, Pierre
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p. 699 - 704
(2007/10/02)
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- Organphosphorus Compounds. XVIII. Synthesisi of 2-Phenyl-2,3-dihydro-1H-1,2-benzazaphosphole 2-Sulfide by Pyrolysis of (2-Aminobenzyl)phenyldithiophosphonic Acid
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Reaction of 2-phthalimidobenzyl bromide (12b) with the dialkyl phenylphosphonites (13a-c) afforded the corresponding alkyl phosphinates (14a-c) which upon hydrazinolysis yielded the respective (2-aminobenzyl)phenylphosphinates (16a-c).Reduction of the phosphinates (16a) or (16b) with lithium aluminium hydride gave (2-aminobenzyl)phenylphosphine (15), characterized by its conversion into crystalline 2,3-diphenyl-1,2,3,4-tetrahydro-1,3-benzazaphosphorine (18). (2-Aminobenzyl)phenylphosphine (15) was heated with sulfur in benzene under reflux for 30 min to give 80percent of (2-aminobenzyl)phenyldithiophosphinic acid (20) which when heated between 100-200 deg in vacuum underwent elimination of hydrogen sulfide to yield 2-phenyl-2,3-dihydro-1H-1,2-benzazaphosphole 2-sulfide (22a).Several other new phosphorus compounds are described.An attempt to prepare a 1H-1,2-benzazaphosphole derivative by photolysis of methyl benzylphosphonic azide (7) was unsuccessful.
- Collins, David J.,Drygala, Peter F.,Swan, John M.
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p. 2095 - 2110
(2007/10/02)
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- The Reaction of 1-Substituted 3,4-Dimethyl-Δ3-phospholens with Diethyl Peroxide: a Correlation Between Rate and 31P Nuclear Magnetic Resonance Shift
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The reactions of a variety of 1-X-3,4-dimethyl-Δ3-phospholens (where X=Br, Me, Ph, NMe2, SEt, H, and OR) with diethyl peroxide are described.The rates of reaction show a broad correlation with the 31P n.m.r. chemical shifts of the starting phospholens, with low field shifts corresponding to the highest reactivity.The results are discussed in terms of the biphilic mechanism for the reaction of trico-ordinate phosphorus compounds with weak ?-bonds.
- Hammond, Philip J.,Scott, Graham,Hall, C. Dennis
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p. 205 - 210
(2007/10/02)
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