87532-69-2Relevant articles and documents
Reduction of CO2 and SO2 with low valent nickel compounds under mild conditions
Gonzalez-Sebastian, Lucero,Flores-Alamo, Marcos,Garcia, Juventino J.
, p. 9116 - 9122 (2011)
The reaction of [(dippe)Ni(μ-H)]2 (A) (dippe = 1,2-bis(diisopropyl-phosphinoethane) with CO2 in toluene afforded the carbonyl nickel(0) compounds of the type {(dippe)Ni(CO)]2(μ- dippe)}(1) and (dippe)Ni(CO)(dippeO)] (2), which were characterized by standard spectroscopic methods; complex (1) was also characterized by single crystal X-ray diffraction. Reaction of (A) with SO2 yields the thiosulfate nickel(ii) compound [Ni(dippe)(S2O3)] (5), which was fully characterized by standard spectroscopic methods and X-ray crystallography. In both cases, a reduction reaction of CO2 to CO and SO2 to S2O32- with (A) took place under mild conditions.
Mn(i) organometallics containing the iPr2P(CH2)2PiPr2 ligand for the catalytic hydration of aromatic nitriles
Gardu?o, Jorge A.,Arévalo, Alma,Flores-Alamo, Marcos,García, Juventino J.
, p. 2606 - 2616 (2018/05/30)
The first example of a homogeneous hydration of aromatic nitriles catalyzed by manganese molecular compounds is reported. The Mn(i) organometallics fac-[(CO)3Mn(dippe)(Z)]1-nX1-n (n = 0, 1; Z = Br, OTf, PhCN; X = OTf) were synthesized and characterized, and their reactivity was studied. The species fac-[(CO)3Mn(dippe)(OTf)] (2) was used as a catalyst precursor for the selective hydration of benchmark benzonitrile (2 mol% 2, THF/H2O 1:2 v/v, 18 h, 100 °C) to produce benzamide in 90% isolated yield. A series of (hetero)aromatic nitriles were hydrated to synthesize the corresponding amides in very good to excellent yields (88-94%). Isotopic labeling studies accounted for a proton transfer as the rate-determining step.
Substitutional lability of diphosphine ligands in tetrahedral iron(II) chloro complexes
Langer, Robert,B?nisch, Friedrich,Maser, Leon,Pietzonka, Clemens,Vondung, Lisa,Zimmermann, Thomas Philipp
, p. 141 - 148 (2015/01/30)
A series of iron(II) dihalogenide complexes with two different bisphosphinoethane ligands is reported. In the case of 1,2-bis(diphenylphosphanyl)ethane (dppe), depending on the stoichiometry, the tetrahedral [(μ-dppe)FeCl2]n and octahedral trans-[(dppe)2FeCl2] complexes are formed. The polymeric complex [(μ-dppe)FeCl2]n, with iron in a tetrahedral environment, preferentially reacts with chelating amines to give the octahedral diphosphine complex, trans-[(dppe)2FeCl2], and different octahedral amine complexes. With the sterically more demanding 1,2-bis(diisopropylphosphanyl)ethane (dippe), the monomeric and tetrahedral halogen complexes [(dippe)FeX2] are exclusively obtained (X = Cl, Br). These complexes react with chelating amines in a similar manner, to give free ligand and the corresponding octahedral amine complex. The present results suggest that the diphosphines in the investigated iron(II) complexes are bound too weakly to form productive catalyst precursors.
A convenient synthetic protocol to 1,2-bis(dialkylphosphino)-ethanes
Doyle, Laurence R.,Heath, Alex,Low, Choon Heng,Ashley, Andrew E.
supporting information, p. 603 - 608 (2014/05/20)
1,2-Bis(dialkylphosphino)ethanes are readily prepared from the parent phosphine oxides, via a novel sodium aluminium hydride/sodium hydride reduction protocol of intermediate chlorophosphonium chlorides. This approach is amenable to multi-gram syntheses, utilises readily available and inexpensive reagents, and benefits from a facile non-aqueous work-up in the final reductive step.
Easily available nickel complexes as catalysts for the intermolecular hydroamination of alkenes and alkynes
Reyes-Sanchez, Adan,Garcia-Ventura, Ilnett,Garcia, Juventino J.
, p. 1762 - 1768 (2014/01/06)
A series of nickel complexes of the type [(P-P)NiX2] ((P-P) = bisphospines or bisphosphites, X = chloride, triflate) were used as catalysts for the hydroamination of both activated and unactivated alkenes and alkynes with pyrrolidine. In general, the use of activated unsaturations, such as acrylonitrile, required mild reaction conditions (e.g. 100 °C and 4 h) in comparison with other non-activated alkenes. Particularly with a series of alkynes, the use of nickel(ii) centers diminished or even inhibited the formation of otherwise undesired homocoupling and/or transfer hydrogenation by-products, such as the ones obtained in the presence of zerovalent nickel. When using less activated substrates, better selectivity was obtained, although harsher reaction conditions were needed. From a general perspective, the results of this report strongly support the potential use of nickel as a good candidate for further application in the hydroamination of organic unsaturations by means of screening of several π acceptor ligands. The Royal Society of Chemistry.
Synthesis and reactivity studies on alkyl-aryloxo complexes of nickel containing chelating diphosphines: Cyclometallation and carbonylation reactions
Cámpora,López,Maya,Palma,Carmona,Valerga
, p. 331 - 341 (2007/10/03)
Nickel alkyl-aryloxo complexes of composition Ni(R)(O-C6H3-2,6-Me2)(P-P) (R = CH2SiMe3, CH3, CH2CMe2Ph; CH2CMe2Ph) complexes undergo a cyclometallation reaction that leads to the metallacycles Ni(CH2CMe2-o-C6H4)(P-P) together with 2,6-dimethylphenol. The alkyl-aryloxo complexes cleanly react with carbon monoxide giving products resulting from CO insertion and reductive elimination, i.e. Ni(CO)2(P-P) and the corresponding 2,6-dimethylphenyl carboxylates quantitatively.
Synthesis of 1,2-bis[(diorgano)phosphino]ethanes via Michaelis-Arbuzov type rearrangements
Baldwin, Lawrence C,Fink, Mark J
, p. 230 - 238 (2007/10/03)
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.
Process for the preparation of substituted aromatic compounds
-
, (2008/06/13)
A process for the preparation of a substituted aromatic compound in which a chloroaromatic compound and an alkyl-, alkenyl- or aryl-boronic acid ester or anhydride are coupled in the presence of palladium and a lipophilic aliphatic phosphine comprising at least one branched aliphatic group or a lipophilic aliphatic Dis(phosphine). Preferred phosphines include triisopropyl, triisobutyl and tricyclohexylphosphine.
Co-condensation of Molybdenum Atoms with the Bulky Tertiary Diphosphine 1,2-Bis(di-isopropylphosphino)ethane: the Molecular Structure of i2PCH2CH2PPri2)2>
Cloke, F. Geoffrey N.,Gibson, Vernon C.,Green, Malcolm L. H.,Mtetwa, Victor S. B.,Prout, Keith
, p. 2227 - 2230 (2007/10/02)
Co-condensation of molybdenum atoms with the tertiary diphosphine 1,2-bis(di-isopropylphosphino)ethane affords the stereochemically non-rigid, eight-co-ordinate tetrahydride complex i2PCH2CH2PPri2)2>.The crystal structure has been determined in the orthorhombic space group Ccca (no. 68), with cell parameters a=18.351(2), b=20.164(2), c=9.150(6) Angstroem, and Z=4.
Intermediates in the Palladium-Catalysed Reactions of 1,3-Dienes, Part 5. Butadiene Complexes of Nickel, Palladium and Platinum
Benn, R.,Jolly, P. W.,Joswig, T.,Mynott, R.,Schick, K.-P.
, p. 680 - 691 (2007/10/02)
A series of complexes of Ni, Pd and Pt has been prepared and their structures investigated NMR-spectroscopically.The nickel and palladium complexes, irrespective of the substituents at phosphorus, contain a fluxional η2-bonded butadiene molecule.In the case of platinum the bonding mode is ligand dependent: an η2-arrangement is observed where R is tert-butyl or cyclohexyl while when R is isopropyl the butadiene adopts an η1,η1-arrangement to give a platinacyclopentene derivative. - Keywords: Nickel-organo Complex, Palladium-organo Complex, Platinum-organo Complex, Butadiene Complex
