- Reactions of Ferrocenium Hexafluorophosphate with P?OR Nucleophiles Give Ring C?H Functionalization or Ring Replacement Products Depending on the Phosphorus Reagent
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Ferrocenium hexafluorophosphate reacts with different P?OR nucleophiles (PR3) in CH2Cl2 at room temperature to give either half-sandwich complexes [CpFe(PR3)3](PF6) (PR3=P(OMe)3, P(OEt)3, PhP(OMe)2) or ferrocenylphosphonium salts [CpFe(C5H4PR3)](PF6) (PR3=iPr2P(OMe), iPr2P(OEt)). Mixtures of both products are formed for some other nucleophiles (PR3=Ph2P(OMe), Ph2P(OEt), PhP(OiPr)2). The mechanism of the former reaction was established using DFT calculations. This reaction pathway is especially characteristic of π-acceptor nucleophiles, which is presumably explained by their ability to stabilize the 19e intermediates. The result of the reaction with tertiary phosphines, aminophosphines, and P?OR nucleophiles can be reliably predicted based on the values of the Tolman electronic parameter (below 2070 cm?1 – only ferrocenylphosphonium salt, in between 2073 cm?1 and 2080 cm?1 – only half-sandwich complex, and in the range from 2070 cm?1 to 2073 cm?1 – mixtures of both products).
- Chamkin, Aleksandr A.,Krivykh, Vasily V.,Kreindlin, Arkady Z.,Dolgushin, Fedor M.,Ustynyuk, Nikolai A.
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p. 1601 - 1610
(2021/04/16)
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- Syntheses und NMR-Spektren phosphororganischer Antioxidantien und verwandter Verbindungen
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The syntheses of various aliphatic, aromatic, sterically hindered, and cyclic organophosphorus compounds (phosphorous acid esters, esters chlorides and ester amides, hydrogen phosphites, phosphinates and phosphates) are reported, and general procedures for preparation are given.The compounds synthesized were investigated by means of 31P-, 1H- and 13C-n.m.r. spectroscopy, and the chemical shifts measured are listed.
- Koenig, T.,Habicher, W.D.,Haehner, U.,Pionteck, J.,Rueger, C.,Schwetlick, K.
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p. 333 - 349
(2007/10/02)
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- LES PHOSPHORANES MONOCYCLIQUES A LIAISON PH DANS LES REACTIONS DE REDISTRIBUTION DE LIGANDS DES COMPOSES DU PHOSPHORE TRICOORDONNE
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The oxidative addition of alcohols and amines with 2-alkyl, 2-aryl, 1,3,2-dioxa, oxaza or diazaphospholanes, leads to a ring opening reaction and ligands exchange around the phosphorus atom by alcoholysis or aminolysis of P-O or P-N bonds.In nearly all cases, monocyclic phosphoranes with P-H bond have been detected in an intermediate step during the exchange of one tricoordinate form to another one.At last we have discussed the phorpholanyl ring stability. - Key words: 1,3,2-Dioxaphospholanes; 1,3,2-oxaza-phospholanes; 1,3,2-diazaphospholanes; Monocyclic phosphoranes with P-M bonds; phosphoranyl ring stability.
- Tangour, B.,Malavaud, C.,Boisdon, M. T.,Barrans, J.
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p. 189 - 196
(2007/10/02)
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- SILICON-PHOSPHORUS ANALOGIES. NUCLEOPHILIC CATALYSIS IN THE ALCOHOLYSIS OF CHLOROPHOSPHORUS DERIVATIVES
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The mechanism of the alcoholysis of chlorophosphonates and chlorophosphates in presence of nucleophilic catalysts like hexamethylphosphotriamide, pyridine and N-methylimidazole is discussed on the basis of kinetic and stereochemical results.We have proposed a mechanism for the reaction, which is governed by entropy, involving reaction of the alcohol with a pentacoordinated intermediate.This accounts for the differences in the stereochemical outcome and the rate equation which can be derived for the reaction with a variety of substrates in addition to the absence of common ion + solvent effects observed.
- Corriu, Robert J. P.,Lanneau, Gerard F.,Leclercq, Dominique
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p. 1959 - 1974
(2007/10/02)
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- The Kinetics and Mechanism of the Reactions of Acyclic Trico-ordinate Phosphorus Compounds with Diethyl Peroxide
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The kinetics of the reactions of acyclic phosphinites, phosphonites, and phosphines with diethyl peroxide in benzene or acetonitrile as solvent are reported together with the activation parameters for phosphinites and phosphonites and Hammett ρ values for all three types of trico-ordinate phosphorus.The data reveal a bimolecular, non-polar transition state for each reaction with ρ values are virtually independent of the nature of the trico-ordinate phosphorus species.
- Lloyd, John R.,Lowther, Nicholas,Hall, C. Dennis
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p. 245 - 250
(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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