cas 1663-45-2, 1,2-Bis(diphenylphosphino)ethane

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Poulin et al.
p. 87,88-92
(1975)
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PH-Switchability and Second-Order Nonlinear Optical Properties of Monocyclopentadienylruthenium(II)/iron(II) Tetrazoles/Tetrazolates: Synthesis, Characterization, and Time-Dependent Density Functional Theory Calculations
Tetrazole/tetrazolate monocyclopentadienyliron(II) and ruthenium(II) compounds of general formulas [(η5-C5H5)M(dppe)(N4(H)CC6H4NO2)][PF6]/[(η5-C5H5)M(dppe)(N4CC6H4NO2)] were investigated for their pH-switching second-order nonlinear optical (SONLO) properties. Compounds [(η5-C5H5)M(dppe)(N4CC6H4NO2)] (M = Fe, Ru) and compound [(η5-C5H5)Ru(dppe)(N4(H)CC6H4NO2)][PF6] were fully characterized by (1H-, 13C-, 31P-) NMR, cyclic voltammetry, and elemental analysis, and compounds [(η5-C5H5)Fe(dppe)(N4CC6H4NO2)] and [(η5-C5H5)Ru(dppe)(N4(H)CC6H4NO2)][PF6] were further characterized by single-crystal X-ray diffraction; the synthesis of [(η5-C5H5)Fe(dppe)(N4(H)CC6H4NO2)][PF6] was unsuccessful. Time-dependent density functional theory calculations were performed using PBE0 and CAM-B3LYP functionals to evaluate the first hyperpolarizability (βtot) of the tetrazole/tetrazolate complexes and for a detailed analysis of the experimental data. Both functionals predict (i) high first hyperpolarizabilities for the tetrazolate complexes [(η5-C5H5)M(dppe)(N4CC6H4NO2)], with βtot[Ru] ≈ 1.2βtot[Fe], and (ii) a 3-fold reduction in βtot[Ru] upon protonation, in complex [(η5-C5H5)Ru(dppe)(N4(H)CC6H4NO2)]+, forecasting [(η5-C5H5)Ru(dppe)(N4CC6H4NO2)]/[(η5-C5H5)Ru(dppe)(N4(H)CC6H4NO2)]+ complexes as on/off, pH-switchable SONLO forms.
Florindo, Pedro R.,Costa, Paulo J.,Piedade,Robalo, M. Paula
p. 6849 - 6863
(2017)
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King et al.
p. 2353,2354
(1968)
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Grubbs et al.
p. 3863
(1977)
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Schindlbauer,Hilzensauer
p. 961,963, 964
(1965)
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Structure of diiodine adducts of some di- and tri-tertiaryphosphines in the solid state and in solution
A series of ditertiaryphosphine-tetraiodine adducts R2P(I2)(CH2)nP(I2)R 2 (R = Ph, n = 1-4; R = PhCH2 or o-CH3C6H4, n = 2) and two tritertiaryphosphine-hexaiodine adducts, PhP(CH2CH2PPh2)2I6 and CH3C(CH2-PPh2)3I6 have been prepared and characterised by 31P-{H} solution NMR and Raman spectroscopy. In the case of Ph2P(I2)(CH2)nP(I 2)Ph2 (n = 2 or 4), 31P-{H} NMR magic angle spinning NMR spectroscopy has been used to investigate the nature of the compounds in the solid state. In agreement with our previous extensive studies on the monophosphine derivatives, R3PI2, the tetraiododiphosphine compounds Ph2P(I2)(CH2)nP(I 2)Ph2 (n = 2 or 4) isolated from diethyl ether contain molecular four-co-ordinate phosphorus centres onto which the diiodine is bound as a linear spoke, as indicated by their 3IP-{H} NMR shifts obtained in CDCl3 solution. Again, in agreement with our previous solution studies of the monophosphine derivatives R3PI2, the diphosphine-tetraiodine adducts completely ionise in CDCl3 solution to produce the ionic compounds [R2P(I)(CH2)nP(I)R2]2I; the solution 31P-{H} NMR shifts are very similar to analogous solution shifts previously assigned to [R3PI]I. The Raman band assignable to v(P-I) has been identified for the compounds and a further band at lower frequency has been observed and assigned to v(I-I). Although the solid-state NMR spectra of the triphosphine-hexaiodine adducts were not recorded, a band assignable, to v(I-I) was observed in the Raman spectrum, suggesting the molecular four-co-ordinate spoke structure also prevails for these hexaiodotritertiaryphosphine compounds in the solid state. From solution 31P-{H} NMR shifts these adducts also appear to ionise in CDCl3 solution.
Bricklebank, Neil,Godfrey, Stephen M.,McAuliffe, Charles A.,Deplano, Paula,Mercuri, Marie L.,Sheffield, Joanne M.
p. 2379 - 2382
(1998)
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Zingales,Graziani,Belluco
p. 256
(1967)
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Aguiar,Beisler
p. 1660
(1964)
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Tibbetts,Brown
p. 3031
(1970)
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A mild and efficient CsOH-promoted synthesis of ditertiary phosphines
A mild and efficient method for the synthesis of ditertiary phosphines has been developed. In the presence of cesium hydroxide, molecular sieves, and DMF, various dihalides were coupled with diphenylphosphine at room temperature, and the results have demonstrated that this methodology offers a general synthetic procedure producing a variety of ditertiary phosphines in high yields.
Honaker, Matthew T.,Salvatore, Ralph Nicholas
p. 277 - 283
(2004)
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The Trityl-Cation Mediated Phosphine Oxides Reduction
Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information
p. 3035 - 3043
(2021/05/10)

A Mild One-Pot Reduction of Phosphine(V) Oxides Affording Phosphines(III) and Their Metal Catalysts
The metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum chemical calculations support the attack of the dissociated chloride anion of intermediated phosphonium salt at the silicon of the disilane as the rate-limiting step for deprotection. The exquisite purity of the resultant phosphine(III) ligands after the simple removal of volatiles under reduced pressure circumvents laborious purification prior to metalation and has permitted the facile formation of important transition metal catalysts.
Kapu?niak, ?ukasz,Plessow, Philipp N.,Trzybiński, Damian,Wo?niak, Krzysztof,Hofmann, Peter,Jolly, Phillip Iain
p. 693 - 701
(2021/04/06)

Reversing Lewis acidity from bismuth to antimony
Investigations on the boundaries between the neutral and cationic models of (Mesityl)2EX (E = Sb, Bi and X = Cl?, OTf?) have facilitated reversing the Lewis acidity from bismuth to antimony. We use this concept to demonstrate a higher efficiency of (Mesityl)2SbOTf(Mesityl)2BiOTf in the catalytic reduction of phosphine oxides to phosphines. The experiments supported with computations described herein will find use in designing new Lewis acids relevant to catalysis.
Balasubramaniam, Selvakumar,Jemmis, Eluvathingal D.,Kumar, Sandeep,Sharma, Deepti,Venugopal, Ajay
supporting information
p. 8889 - 8892
(2021/09/10)

Preparation technology of bis(dibenzyl)phosphorane
The invention provides a preparation technology of bis(dibenzyl)phosphorane and belongs to the technical field of synthesis of organic matters. The technology comprises the following steps: taking metallic lithium, triphenylphosphine and water to react to generate dibenzylphosphorane; taking the dibenzylphosphorane to react with dihalogenohydrocarbon to generate the bis(dibenzyl)phosphorane. According to a production technology, an intermediate product and an intermediate byproduct do not need to be separated; the technology is simple in technological operation, low in raw material cost and high in yield and can be used for producing the low-cost and high-quality bis(dibenzyl)phosphorane.
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(2019/08/06)

Mild Reduction of Phosphine Oxides with Phosphites To Access Phosphines
A new method for the iodine-catalyzed reduction of phosphine oxides with phosphites at room temperature is reported. The mild reaction conditions, scalability, and simple purification requirements render it a method of choice for the large-scale production and facile regeneration of a variety of phosphines. Mechanistic studies, supported by DFT calculations of the oxygen transfer between the starting phosphine oxide and the phosphite reagent, are also presented. Such transmutations of phosphorus species were previously unknown.
Li, Peng,Wischert, Raphael,Métivier, Pascal
supporting information
p. 15989 - 15992
(2017/11/01)

Synthesis of bis(trithio)phosphines by oxidative transfer of phosphorus(i)
The synthesis of novel bis(trithio)phosphines is achieved by oxidative addition of tetrathiocins to the phosphorus(i) reagent [PIdppe][Br] in good yields under ambient conditions. These bis(trithio)phosphines and the related intermediate diphosphine species are characterized by X-ray diffraction and multinuclear NMR and a mechanism is proposed for the formation of these molecules. In contrast, the related reaction with diphenyldisulfide produces a mononuclear tris(phenylthio)phosphine.
Kosnik, Stephanie C.,Nascimento, Maxemilian C.,Rawson, Jeremy M.,Macdonald, Charles L. B.
p. 9769 - 9776
(2017/08/10)

Raney-Ni reduction of phosphine sulfides
A variety of tertiary phosphine sulfides have been reduced by Raney-Ni to give the corresponding phosphineswith high efficiency and undermild conditions. Alkyl, aryl, acyclic, cyclic, aswell as sterically crowded phosphine sulfides are reduced with equal facility. Optically active P-stereogenic phosphine sulfides are reduced stereospecifically with clean retention of configuration at P. Reductions of unsaturated phosphinesulfides is not fully chemoselective and takes place with concomitant partial reduction of the double bond. Clean reduction of the unsaturated phosphine sulfides to the corresponding fully saturated phosphines can be achieved in one step by running the reduction under H2atmosphere (balloon).
Demchuk, Oleg M.,?wierczyńska, Wioletta,Dziuba, Kamil,Frynas, S?awomir,Flis, Anna,Pietrusiewicz, K. Micha?
p. 64 - 68
(2016/12/24)

Chemoselective Reduction of Phosphine Oxides by 1,3-Diphenyl-Disiloxane
Reduction of phosphine oxides to the corresponding phosphines represents the most straightforward method to prepare these valuable reagents. However, existing methods to reduce phosphine oxides suffer from inadequate chemoselectivity due to the strength of the P=O bond and/or poor atom economy. Herein, we report the discovery of the most powerful chemoselective reductant for this transformation to date, 1,3-diphenyl-disiloxane (DPDS). Additive-free DPDS selectively reduces both secondary and tertiary phosphine oxides with retention of configuration even in the presence of aldehyde, nitro, ester, α,β-unsaturated carbonyls, azocarboxylates, and cyano functional groups. Arrhenius analysis indicates that the activation barrier for reduction by DPDS is significantly lower than any previously calculated silane reduction system. Inclusion of a catalytic Br?nsted acid further reduced the activation barrier and led to the first silane-mediated reduction of acyclic phosphine oxides at room temperature.
Buonomo, Joseph A.,Eiden, Carter G.,Aldrich, Courtney C.
supporting information
p. 14434 - 14438
(2017/10/23)

Highly efficient reduction of tertiary phosphine oxides and sulfides with amine-assisted aluminum hydrides under mild conditions
Reduction of tertiary phosphine oxides and sulfides into the corresponding phosphines with amine-assisted aluminum hydrides has been studied. The method is characterized by mild conditions, short reaction time, high efficiency, and expanded substrate scope. The new method is an alternative to the currently used methods of reducing phosphine oxides or recycling phosphines engaged in organic reactions.
Yang, Shuyan,Han, Xinxin,Luo, Minmin,Gao, Jing,Chu, Wenxiang,Ding, Yuqiang
p. 1156 - 1160
(2015/06/30)

Ethylene oligomerization catalyst systems having enhanced selectivity
Disclosed herein is a catalyst system for selective oligomerization of ethylene, which comprises a P—C—C—P frame-work ligand, which is (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4), and a chromium-based metal compound. Also disclosed is a method of greatly enhancing the activity and selectivity of oligomerization, such as trimerization or tetramerization, using a ligand having a specific steric arrangement structure.
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(2013/02/27)

Highly chemoselective metal-free reduction of phosphine oxides to phosphines
Unprecedented chemoselective reductions of phosphine oxides to phosphines proceed smoothly in the presence of catalytic amounts of specific Br?nsted acids. By utilizing inexpensive silanes, e.g., PMHS or (EtO)2MeSiH, other reducible functional groups such as ketones, aldehydes, olefins, nitriles, and esters are well-tolerated under optimized conditions.
Li, Yuehui,Lu, Liang-Qiu,Das, Shoubhik,Pisiewicz, Sabine,Junge, Kathrin,Beller, Matthias
p. 18325 - 18329
(2013/01/15)

ETHYLENE TETRAMERIZATION CATALYST SYSTEMS AND METHOD FOR PREPARING 1-OCTENE USING THE SAME
Disclosed herein is a method of preparing 1-octene at high activity and high selectivity while stably maintaining reaction activity by tetramerizing ethylene using a chromium-based catalyst system comprising a transition metal or a transition metal precursor, a cocatalyst, and a P—C—C—P backbone structure ligand represented by (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4).
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Page/Page column 9

(2010/06/16)

A catalytic method for the reduction of secondary and tertiary phosphine oxides
TMDS has been found to be an efficient hydride source for the reduction of tertiary and secondary phosphine oxides using a catalytic amount of Ti(Oi-Pr)4. All classes of tertiary phosphine oxides, such as triaryl, trialkyl, and diphosphine, were effectively reduced. Georg Thieme Verlag Stuttgart.
Berthod, Mika?l,Favre-Réguillon, Alain,Mohamad, Jahjah,Mignani, Gérard,Docherty, Gordon,Lemaire, Marc
p. 1545 - 1548
(2008/02/05)

Work-up-free deprotection of borane complexes of phosphines, phosphites, and phosphinites with polymer-supported amines
Borane complexes of phosphorus compounds, a very common oxidation-free relay for catalytic ligands (phosphines, phosphites, and phosphinites), can be easily deprotected by treatment with polymer-supported piperazine or N-methylpiperazine. Deprotection conditions have been optimized for the different types of phosphorus compounds, and the resulting solutions can be used without any intermediate work-up or purification process. Georg Thieme Verlag Stuttgart.
Sayalero, Sonia,Pericàs, Miquel A.
p. 2585 - 2588
(2008/09/16)

CsOH-promoted P-alkylation: A convenient and highly efficient synthesis of tertiary phosphines
A mild and efficient method for the synthesis of tertiary phosphines and ditertiary phosphines has been developed. In the presence of cesium hydroxide, molecular sieves and DMF at room temperature, various secondary phosphines and alkyl bromides were examined, and the results have demonstrated that this methodology offers a general synthetic procedure to produce tertiary phosphines in moderate to high yields. Optically active tertiary phosphine synthesis is also described.
Honaker, Matthew T.,Sandefur, Benjamin J.,Hargett, James L.,McDaniel, Alicia L.,Salvatore, Ralph Nicholas
p. 8373 - 7377
(2007/10/03)

Synthesis of 1,2-bis[(diorgano)phosphino]ethanes via Michaelis-Arbuzov type rearrangements
A three-step process for the synthesis of the bis(diorganophosphino)ethanes R2PCH2CH2PR2 where R = Et, Ph, iPr, Cy and tBu was examined. In the first step, diorganochlorophosphines were allowed to react with ethylene glycol in the presence of triethylamine at room temperature in THF solution. For R = Ph, iPr and Cy, the bisphosphinites R2POCH2CH2OPR2 were obtained in high yield. For R = Et, the bisphosphinite could not be isolated but may be formed in 80% mixtures with tetraethyldiphosphine, Et2PPEt2, as a minor component. The reaction of di-t-butylchlorophosphine with ethylene glycol occurs at temperatures greater than 130 °C giving di-t-butyl phosphine oxide, tBu2PH(O), as the only phosphorus-containing product. Thermolysis of the bisphosphinites R2POCH2CH2OPR2 (R = Ph, iPr and Cy) at 190-260 °C for 24 h gave the bisphosphine oxides, R2P(O)CH2CH2(O)PR2 in 9% (Ph), 90% (iPr) and 93% (Cy) yields. A DSC study of the thermal rearrangement of Cy2POCH2CH2OPCy2 to Cy2P(O)CH2CH2(O)PCy2 yielded an enthalpy of isomerization of -40.4 ± 0.6 kcal mol-1. Reduction of the bisphosphine oxides, R2P(O)CH2CH2(O)PR2 (R = Ph, iPr and Cy) with trichlorosilane gave the bisphosphines, R2PCH2CH2PR2 in 80-85% yield. The overall yields of the bisphosphines R2PCH2CH2PR2 (R = iPr and Cy) in the three-step process were 61 and 75%, respectively, suggesting that this process should be an attractive synthetic pathway to these two bisphosphines.
Baldwin, Lawrence C,Fink, Mark J
p. 230 - 238
(2007/10/03)

t-BuOK-catalyzed addition phosphines to functionalized alkenes: A convenient synthesis of polyfunctional phosphine derivatives
The use of t-BuOK in DMSO allows a smooth addition of Ph2PH, Cy2PH and Ph2P(O)H to various functionalized alkenes leading to polyfunctional phosphines in good yields. This method has been used to prepare precursors for P,P- and P,N-ligands.
Bunlaksananusorn, Tanasri,Knochel, Paul
p. 5817 - 5819
(2007/10/03)

Stereospecific reduction of phosphine oxides to phosphines by the use of a methylation reagent and lithium aluminum hydride
(equation presented) Various phosphine oxides are efficiently reduced by the use of a methylation reagent and lithium aluminum hydride. Optically active P-chirogenic phosphine oxides are also reduced with inversion of configuration at phosphorus atom by treatment with methyl triflate, followed by reaction with LiAlH4.
Imamoto, Tsuneo,Kikuchi, Shin-Ichi,Miura, Tomoya,Wada, Yoshiyuki
p. 87 - 90
(2007/10/03)

Preparation of organohalosilanes
When oganohalosilanes are prepared by charging a reactor with a contact mass containing a metallic silicon powder and a copper catalyst, and introducing an organohalide-containing gas into the reactor to effect the direct reaction, a poly(organo)phosphino compound is added to the contact mass. The invention is successful in producing organohalosilanes at a significantly improved production rate without reducing the selectivity of useful silane.
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(2008/06/13)

Method for producing benzoic acid derivatives
The invention relates to a method for producing a benzoic acid derivative represented by the general formula (1). The method includes the step of reacting an aromatic compound represented by the general formula (2), with carbon monoxide and a hydroxy compound (i.e., water or an alcohol), in the presence of (a) a metal compound containing a metal of 8, 9 and 10 groups of periodic table, (b) a first phosphine derivative represented by the general formula (R1)2P—Q—P(R1)2, and (c) a base, It is possible to easily and efficiently produce the benzoic acid derivative by the method.
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(2008/06/13)

Organometallic chemistry on a metallathiaborane cluster: Reactions of [8,8-(PPh3)2-nido-8,7-RhSB9H10] with bidentate phosphine ligands
Reactions of the unsaturated cluster [8,8-(PPh3)2-nido-8,7-RhSB9H10] (1) with the bidentate 1,n-bis(diphenylphosphino)alkanes (CH2)n(PPh2)2, where n = 1-3 (abbreviated as dppm, dppe, and dppp, respectively), have been studied. When a 1:1 molar ratio of phosphine to rhodathiaborane is used, for dppe and dppp, simple substitution to form [8,8-(η2-dppe)-nido-8,7-RhSB9H10] (2) or [8,8-(η2-dppp)-nido-8,7-RhSB9H10] (3) is observed. However, in the presence of an excess of dppe or dppp, mixtures of the species 2 and [8,8-(η2-dppe)-9-(η1-dppe)-nido-8,7-RhSB 9H10] (4) or of 3 and [8,8-(η2-dppp)-9-(η1-dppp)-nido-8,7-RhSB 9H10] (5) are formed, respectively. Under both sets of conditions, when dppm is used, only one product, [8,8-(η2-dppm)-8-(η1-dppm)-nido-8,7-RhSB 9H10] (6), is observed. This latter species has two dppm ligands coordinating to the metal, one in a unidentate mode and the other bidentate. Species 2 and 3 are formally unsaturated, two electrons short of the number required for the observed 11-vertex nido structure. In contrast, 4 and 5 are saturated with the cage-bonded unidentate ligand providing an additional skeletal electron pair to the cluster. The species 4 and 5 are unstable in solution; depending on the conditions, they dissociate to give free phosphine and the chelate 2 or 3 or they undergo nido to closo transformation with loss of dihydrogen, affording the corresponding 11-vertex closo compounds [1,1-(η2-dppe)-3-(η1-dppe)-closo-1,2-RhSB 9H8] (17) and the dppp analogue [1,1-(η2-dppp)-3-(η1-dppp)-closo-1,2-RhSB 9H8] (18). Further reaction in the case of 5 allows isolation of the linked cluster system [{1,1-(η2-dppp)-closo-1,2-RhSB9H8} 2-3,3′-(μ-dppp)] (19). The species have been characterized by NMR and mass spectrometry, and crystal structure determinations are described for 3, the OEt derivative of 3, [8,8-(η2-dppp)-9-(OEt)-nido-RhSB9H9] (14), 6, and the phosphine oxide of 17, [1,1-(η2-dppe)-3-(η1-dppeO)-closo-1,2-RhSB 9H8] (20).
Macías, Ramón,Rath, Nigam P.,Barton, Lawrence
p. 3637 - 3648
(2008/10/08)

Method for manufacturing acryloxypropysilane
A method to manufacture acryloxypropylsilane to a high degree of purity is achieved by hydrosilation of (A) allyl acrylate or allyl methacrylate by (B) a hydrosilane compound, using (C) a platinum-containing compound as the catalyst and (D) an organic phosphorus compound as the promoter. The acryloxypropylsilane product is expressed by General Formula I where R1 represents a hydrogen or methyl group, R2 represents a hydrolyzable group, R3 represents an aryl, alkenyl or aryl group of carbon number 1-12, and n is 0, 1, 2, or 3.
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(2008/06/13)

An Efficient Procedure for the Synthesis of C-Chiral Bisphosphines.
A practical method for the synthesis of bisphosphines containing homochiral carbon backbones is described.This procedure entails sequential reaction of a homochiral ditosylate with the appropriate dialkyl- or diarylphosphine-borane anion followed by BH3 decomplexation mediated by HBF4*OMe2.
McKinstry, Lydia,Livinghouse, Tom
p. 7655 - 7666
(2007/10/02)

Titanium (IV) catalysis in the reduction of phosphine oxides
Phosphine oxides can be reduced by triethoxysilane, or more conveniently polymethylhydrosiloxane, and catalytic titanium (IV) isopropoxide and provides a system for the efficient one-pot generation of phosphonium salts; the reduction occurs with retention of configuration at phosphorus.
Coumbe, Tristan,Lawrence, Nicholas J.,Muhammad, Faiz
p. 625 - 628
(2007/10/02)

An Efficient Procedure for the Synthesis of Electron Rich Biphosphines Containing Homochiral Backbones.
An eminently practical method for the synthesis of homochiral biphosphines is described.This procedure entails the sequential reaction of homochiral ditosylate with the appropriate dialkylphosphine-borane anion followed by BH3 decomplexation mediated by HBF4*OMe2.
McKinstry, Lydia,Livinghouse, Tom
p. 9319 - 9322
(2007/10/02)

ZUR REAKTION VON PHOSPHORVERBINDUNGEN MIT SCHWESINGER BASEN-I P-C-BINDUNGKNUEPFUNG AN P-H-FUNKTIONELLEN PHOSPHORVERBINDUNGEN
Secondary and tertiary phosphines (RR'PH; R2R'P) may be synthesized by alkylation of primary or secondary phosphines with organo halides (R' = Et, n-C7H15, Bz, Me3Si; X = Cl, Br) in the presence of Schwesinger bases as auxillary bases in high yields.Alkylation of diphenylphosphine with alkylene dihalides and Schwesinger bases affords alkylendiphosphines. Key words: Alkylation; secondary and tertiary phosphines; Schwesinger bases.
Uhlig, Frank,Puschner, Beatrix,Herrmann, Eckhard,Zobel, Bernhard,Bernhardt, Henry,Uhlig, Wolfram
p. 155 - 164
(2007/10/02)

Process for the preparation of ketones
A process for the preparation of ketones which comprises reacting a conjugated diolefin and water in the liquid phase in the presence of a catalyst system comprising: a) a group VIII metal compound, and b) a source of protons.
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(2008/06/13)

Radical Cations of Bis(diphenylphosphino) Derivatives (Ph2P-R-PPh2): The Formation of Localized, Cyclic, and Dimeric Configurations. An ESR and Quantum Chemical Study
A matrix ESR study on radiogenic radical cations of Ph2P-R-PPh2 derivatives with various linkers (R) is presented.The experiments show that in a frozen dichloromethane solution the radical cations can adopt localized (Ph2PR*+), cyclic , and dimeric (Ph2RP*-PRPh2+) configurations, depending on the nature of the linker.The cyclic and dimeric products are formed in the reaction of a localized cation with a second free-electron pair, resulting in an intra- or intermolecular three-electron P-P ?* bond, respectively.The formation of the cyclic structure, with a strongly bent P-P ?* bond, requires a specific proximate position of the two phosphine moieties in the precursor molecule.The mutual orientation of the two free-electron pairs of the precursors is assessed by NMR via the nJPP spin-spin coupling constant.Ab initio UHF quantum chemical calculations at the 3-21G*/SCF level support the assignments.
Janssen, Rene A. J.,Aagaard, Olav M.,Cabbolet, Marcoen J. T. F.,Waal, Bas F. M. de
p. 9256 - 9263
(2007/10/02)

Process for the selective preparation of alkenecarboxylic acid derivatives
A process for the selective carbonylation of a conjugated diene by contacting with carbon monoxide in the presence of a hydroxyl-group-containing compound such as water, alcohol, phenol or carboxylic acid in liquid phase using a catalyst system formed by the combination of: (a) a palladium compound and (b) at least one organic bidentate phosphine.
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(2008/06/13)

Use of Sacrificial Anodes in Electrochemical Functionalization of Organic Halides
This article reviews the new possibilities in organic synthesis offered by the electroreduction of organic halides in the presence of various electrophiles using sacrificial metallic anodes.
Chaussard, Jacques,Folest, Jean-Claude,Nedelec, Jean-Yves,Perichon, Jacques,Sibille, Soline,Troupel, Michel
p. 369 - 381
(2007/10/02)

From Metal Imides and Molecular Nitrogen to Ammonia and Dinitro Complexes
Reduction of a molybdenum imide under molecular nitrogen gives ammonia and a dinitrogen complex.
Mohammed, Modher T.,Pickett, Christopher J.
p. 1119 - 1121
(2007/10/02)

Heat of reaction of (norbornadiene)molybdenum tetracarbonyl with monodentate and bidentate ligands. Solution thermochemical study of ligand substitution in the complexes cis-L2Mo(CO)4
The enthalpy of reaction of (NBD)Mo(CO)4 (NBD = norbornadiene) with a number of monodentate and bidentate ligands forming cis-L2Mo(CO)4 has been measured at 30°C in THF solution. The heats of reaction span a range of 33 kcal/mol. The order of stability for monodentate ligands is PCl3 6H5)3 6H5)3 3 6H5)3 6H5)2(CH3) 6H5)(CH3)2 3)3 3 6H11)NC 3 3. The series of chelating bidentate phosphines R2P-(CH2)nPR2 (n = 1-4, R = C6H5; n = 1, 2, R = CH3) and several related ligands were investigated. The chelating ring systems in the metallacycles show strain energies of about 8 kcal/mol for four-membered rings. The mixed ligand (C6H5)2PCH2CH2-As(C 6H5)2 shows a heat of binding midway between the heats of binding of (C6H5)2PCH2CH2P(C 6H5)2 and (C6H5)2AsCH2C-H2As(C 6H5)2, implying group additivity in this system. The complex (phen)Mo(CO)4 is some 5 kcal/mol more stable than (bpy)Mo(CO)4, presumably due to conformational effects in the free ligand. The ligand 1,5-cyclooctadiene forms a complex 2 kcal/mol less stable than that of norbornadiene. The influences of steric and electronic factors in determining the Mo-L bond strength are discussed.
Mukerjee, Shakti L.,Nolan, Steven P.,Hoff, Carl D.,Lopez De La Vega, Ramon
p. 81 - 85
(2008/10/08)

Reactions between Co(II), 1,2-bis(diphenylphosphino)ethane, and NaBH3CN in the presence and abscence of CO. The crystal structure of bis(cyanotrihydroborato)tetrakis(N,N-dimethylformamide)cobalt(II)
Reactions between Co(II), Diphos, and NaBH3CN lead to Co(BH3CN)2(Diphos)2, 1, orX, 2 (X=CLO4 or BPh4), and, in certain solvents, 2 reacts to produce (ClO4).Compound 1 can be reversibly converted to Co(BH3CN)2(DMF)4, 4, via Co(BH3CN)2(Diphos)(DMF).In addition, 1 reacts with CO to form the Co(I) and Co(III) compounds (CO)>X and X (X=BH3CN or BPh4).Single crystal X-ray diffraction studies of 4 show that the compound crystallizes in the triclinic space group P1, with unit cell parameters a=7.572(6), b=9.695(6), c=9.395(6) A, α=81.06(4), β=68.46(5), γ=68.19(5) deg, V=595.5A3, Z=1, and dcalc=1.202 g cm-3.The structure converged to a conventional R factor of 0.040 for 2841 observations and showed an octahedral arrangement of four O atoms from DMF molecules and two trans N-bound BH3CN groups around the Co(II) center.
Elliot, David J.,Haukilahti, Sanna,Holah, David G.,Hughes, Alan N.,Maciaszek, Stanislaw,et al.
p. 1770 - 1775
(2007/10/02)

Facile rearrangement and electron transfer of 19-electron radicals from the reduction of the bischelated manganese carbonyl cation Mn(CO)2[PPh2(CH2)2PPh 2]2+
The cathodic reduction of the bischelated manganese carbonyl cation trans-Mn(CO)2(η2-DPPE)2+ (I+, where DPPE = PPh2-(CH2)2PPh2) produces the metastable anion Mn(CO)2(η2-DPPE)(η1-DPPE)- (II-) via an overall 2e process at a Pt electrode in either tetrahydrofuran or acetonitrile solution. The unusual observation of a cathodic curve crossing and two isopotential points in the cyclic voltammogram of I+ can be traced to an electron transfer with II- to afford a pair of neutral radicals, i.e., the 19e I? and the 17e II?. The former (which is also generated during the initial step in the reduction of I+) is a metastable species and spontaneously extrudes an end of one DPPE ligand to afford the second radical II? with the rate constant kr ≈ 4 × 106 s-1. The structures of the anionic and radical intermediates II-, II?, and I? are discussed in the context of their transient electrochemical behavior as well as their 31P NMR and ESR spectra. The rather slow rate of electron transfer between I+ and II- is ascribed to steric effects in carbonylmanganese ions encumbered with a pair of DPPE ligands.
Kuchynka,Kochi
p. 2574 - 2581
(2008/10/08)

Antitumor pharmaceutical compositions and methods for treating tumors employing α,ω-bis(disubstitutedphosphino)hydrocarbon derivatives or [α, ω-bis(disubstitutedphosphino)hydrocarbon] di
Antitumor pharmaceutical compositions and methods for treating tumors employing α,ω-bis(disubstitutedphosphino)hydrocarbon derivatives or [α,ω-bis(disubstituted phosphino)hydrocarbon] digold(I), digold(III), disilver(I), and dicopper(I) derivatives are disclosed.
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(2008/06/13)

SYNTHESIS OF TETRIARY PHOSPHINES AND PHOSPHINE OXIDES BY NUCLEOPHILIC ADDITION REACTIONS USING INTERFACIAL CATALYSTS OR SUPERBASIC MEDIA
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Khachatryan, R. A.,Sayadyan, S. V.,Grigoryan, N. Yu.,Indzhikyan, M. G.
p. 2197 - 2203
(2007/10/02)

ELECTROCHEMICAL SYNTHESIS OF TERTIARY PHOSPHINES FROM ORGANIC HALIDES AND CHLOROPHOSPHINES
The electrochemical synthesis of a wide range of tertiary mono- and diphosphines has been achieved in very simple and mild conditions, in an undivided electrolytic cell with a sacrificial anode of magnesium.
Folest, J. C.,Nedelec, J. Y.,Perichon, J.
p. 1885 - 1886
(2007/10/02)

CLEAVAGE OF PHOSPHOROUS-CARBON BONDS WITH SODIUM/NAPHTHALENE. FACILE PREPARATION OF UNSYMMETRICAL DIPHOSPHINES
Sodium/naphthalene was found to be a homogeneous, mild and selective reagent for the reductive cleavage of aryl-phosphorous bonds.Such cleavage reactions are very useful in the convenient synthesis of unsymmetrical diphosphines from commercially available and air-stable diphosphines.
Chou, Ta-Shue,Tsao, Chung-Huang,Hung, Su Chun
p. 53 - 58
(2007/10/02)

A Simple Synthesis and Some Synthetic Applications of Substituted Phosphide and Phosphinite Anions
Based on data for the acidity relationship of phosphines and phosphinous acids and water in dimethyl sulfoxide and water, a simple method is reported for the generation of phosphide and phosphinite anions by the action of concentrated aqueous alkali on primary and secondary phosphines as well as phosphinous acids in dimethyl sulfoxide or other dipolar aprotic solvents.Alkylation of the anion yields secondary and tertiary phosphines, polyphosphines, functionally substituted phosphines as well as similarly substituted phosphine oxides.Phosphinous acids have beenalkylated in various solvents in two-phase systems containing concentrated aqueous alkali and tetrabutylammonium iodide as phase transfer catalyst.
Tsvetkov, E. N.,Bondarenko, N. A.,Malakhova, I. G.,Kabachnik, M. I.
p. 198 - 208
(2007/10/02)

SIMPLE METHOD FOR GENERATING SUBSTITUTED PHOSPHIDE AND PHOSPHINITE ANIONS AND SYNTHESES BASED ON THEM
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Tsvetkov, E. N.,Bondarenko, N. A.,Malakhova, I. G.,Kabachnik, M. I.
p. 8 - 22
(2007/10/02)

HYDRIDE REDUCTION OF THE CATION 5-C5H5)Fe(Ph2PCH2CH2PPh2)CO>PF6; FORMATION OF (η5-C5H5)FeH(CO)(Ph2PCH2CH2PPh2) AND ELIMINATION OF H2 FROM 5-C5H5)FeH(CO)>2(Ph2PCH2CH2PPh2)
(η5C5H5)FeH(CO)(Ph2PCH2CH2PPh2), formed in the LiAlH4 reduction of the cation of 5-C5H5)Fe(Ph2PCH2CH2PPh2)CO>PF6, can be converted into 5-C5H5)FeH(CO)>2(Ph2PCH2CH2PPh2), which undergoes thermal and photochemical elim
Davies, Stephen G.,Hibberd, John,Simpson, Stephen J.,Watts, Oliver
p. C31 - C33
(2007/10/02)

Ditertiary phosphine complexes of nickel. Spectral, magnetic, and proton resonance studies. A planar-tetrahedral equilibrium
A number of complexes of nickel in oxidation states 0, II, and III with the ditertiary phosphines (C6H5)2P(CH2)nP(C 6H5)2 (n = 1, 2, or 3) are reported and studied by spectral and magnetic methods. In solution in organic solvents complexes of the type Ni[(C6H5)2P(CH2)nP(C 6H5)2]X2 where X = Br or I and n = 2 remain diamagnetic. The analogous complexes with n = 3 show a square-planar (diamagnetic)-tetrahedral (paramagnetic) equilibrium in solution. Isotropic proton magnetic resonance shifts were observed in these systems and thermodynamic parameters for the equilibrium were obtained from the temperature dependences of these shifts. The epr spectrum of polycrystalline Ni[(C6H5)2P(CH2)3P(C 6H5)2]Br3 shows an isotropic signal at g = 2.218.
Van Hecke, Gerald R.,Horrocks Jr., William DeW.
p. 1968 - 1974
(2008/10/08)