- Coordination and extraction properties of 1,2-bis(diphenylphosphoryl)-benzene toward f-block element nitrates: Structural, spectroscopic and DFT characterization of the complexes
-
Reaction of 1,2-bis(diphenylpsphoryl)benzene 1,2-[Ph2(O)P]2C6H4 (L) with f-element nitrates resulted in 1:1 and 1:2 complexes. The isolated complexes, namely, [UO2(L)(NO3)2]·MeCN
-
-
Read Online
- Diphosphination of Arynes with Diphosphines
-
A diphosphination of arynes with diphosphines has been developed. The reaction of stable aryne precursors, 2-(trimethylsilyl)aryl triflates, with tetraaryldiphosphines proceeds in the presence of fluorine- or carbonate-based activators to deliver the corresponding diphosphinated products, sterically and electronically tuned 1,2-bis(diphenylphosphino)benzene (dppbz) derivatives, which can find wide application in transition metal catalysis and material science. Additionally, preliminary computational studies on the reaction mechanism are also reported.
- Okugawa, Yuto,Hayashi, Yoshihiro,Kawauchi, Susumu,Hirano, Koji,Miura, Masahiro
-
supporting information
p. 3670 - 3673
(2018/06/26)
-
- Elusive Phosphine Copper(I) Boryl Complexes: Synthesis, Structures, and Reactivity
-
We report the first isolation of phosphine copper boryl complexes - species pivotal to numerous copper-catalyzed borylation reactions. The reaction of diboron(4) derivatives with copper tert-butoxide complexes of phosphine ligands allows the isolation of the dimeric μ-boryl-bridged Cu(I) complexes [(iPr3P)Cu-Bdmab]2 (4) and [(C6H4(Ph2P)2)Cu-Bpin]2 (6) with Cu···Cu distances of 2.24-2.27 ? (dmab = (NMe)2C6H4, pin = (OCMe2)2)). A slightly more sterically demanding boryl ligand furnishes the unprecedented multinuclear copper boryl complex [(iPr3P)2Cu8(B(iPrEn))3(OtBu)3] (5), a potential intermediate of the decomposition of an initial Cu(I) boryl complex (iPrEn = (NiPr)2C2H4). All complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy, and elemental analysis. DFT computations support the nature of these unique complexes and give insight into their electronic structures.
- Borner, Corinna,Anders, Lisa,Brandhorst, Kai,Kleeberg, Christian
-
supporting information
p. 4687 - 4690
(2018/02/07)
-
- A series of dinuclear cuprous iodide complexes chelated with 1,2-bis(diphenylphosphino)benzene derivatives: Structural, photophysical and thermal properties
-
Three new bisphosphine ligands, 4-phenyl-1,2-bis(diphenylphosphino)benzene (Ph-dppb), 4-pyrrolyl-1,2-bis(diphenylphosphino)benzene (Pr-dppb), and 4,5-dimethoxyl-1,2-bis(diphenylphosphino)benzene (OMe-dppb), were synthesized to coordinate with cuprous iodi
- Li, Xiaoyue,Zhang, Juanye,Wei, Feng,Liu, Xiaochen,Liu, Zhiwei,Bian, Zuqiang,Huang, Chunhui
-
p. 4388 - 4394
(2016/07/06)
-
- Ortho-Trialkylstannyl Arylphosphanes by C-P and C-Sn Bond Formation in Arynes
-
A novel and efficient approach to ortho-trialkylstannyl arylphosphanes by the reaction of arynes generated in situ with stannylated phosphanes (R3Sn-PR2) is described. Concurrent C-P and C-Sn bond formation occurs with high yields, and stannylated products are easily transformed into valuable ortho-substituted arylphosphanes. The reaction features high efficiency, good regioselectivity, and excellent practicality.
- Li, Yuanming,Chakrabarty, Shyamal,Mück-Lichtenfeld, Christian,Studer, Armido
-
p. 802 - 806
(2016/02/27)
-
- Organocatalyzed Reduction of Tertiary Phosphine Oxides
-
A novel selective catalytic reduction method of tertiary phosphine oxides to the corresponding phosphines has been developed. Notably, the reaction proceeds smoothly with low catalyst loadings of 1-5 mol% even at low temperature (70 C). Under the optimized conditions various phosphine oxides could be selectively reduced and the desired phosphines were usually obtained in excellent yields above 90%. Furthermore, we have developed a one-pot reaction sequence for the preparation of valuable phosphinborane adducts. Simple addition of BH3THF subsequent to the reduction step gave the desired adducts in yields up to 99%.
- Schirmer, Marie-Luis,Jopp, Stefan,Holz, Jens,Spannenberg, Anke,Werner, Thomas
-
supporting information
p. 26 - 29
(2016/01/25)
-
- Ligand-controlled iron-catalyzed cross coupling of benzylic chlorides with aryl Grignard reagents
-
The selective cross coupling of benzylic chlorides with aryl Grignard reagents has been achieved by using catalytic amounts of FeCl2 and electronically tuned ortho-phenylenebisphosphine ligands. Although electron-deficient ligands promoted the reductive homocoupling of benzylic halides, electron-rich ligands effectively promoted the desired cross-coupling reaction to afford the corresponding diarylmethanes in good to excellent yields.
- Kawamura, Shintaro,Nakamura, Masaharu
-
supporting information
p. 183 - 185
(2013/03/28)
-
- Bisphosphine monoxides with o-phenylene backbones in Pt, Pd and Fe complexes
-
A new route to aromatic bisphosphine monoxides has been explored through ortholithiation of triphenylphosphine oxide and subsequent reaction of the lithiated intermediate with a range of alkyl and aryl phosphine chlorides. Routes to the known bisphosphine monoxide (BMPO) (o-C6H4){P(O)Ph2}PPh2 (2aO) and a range of new BPMOs of the type Ph2P(O)(o-C6H4)PR2 where R2 = iPr2, Cy2, Et2 are described. Reaction of 2aO with MCl2(cod) (M = Pd, Pt; cod = cyclooctadiene) gives products of the form [MCl(κ1-P-2aO)(κ2-P,O-2aO)]+ Cl- and MCl2(κ2-P,O-2aO); the former exhibits fluxional behaviour which has been analysed by 195Pt NMR and 31P variable-temperature NMR spectroscopy. The bidentate complex is not fluxional for either the Pd or the Pt example; the Pt complex PtCl2(κ2-P,O-2aO) has been characterised by X-ray crystallography. By comparison of the product distribution seen by 31P NMR spectroscopy and ESI-MS it was established that the different coordination modes of 2aO result in quite different behaviour of the complexes when studied by ESI-MS; when the O is formally coordinated to the metal its ionisation efficiency is very low. Synthesis of Fe(CO)4(2aO) confirmed the ability of the 2aO ligand to render a neutral complex with no alternative pathways for ionisation to be readily detected by ESI-MS.
- Farrer, Nicola J.,McDonald, Robert,Piga, Toria,McIndoe, J. Scott
-
experimental part
p. 254 - 261
(2010/04/04)
-
- 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).
- -
-
Page/Page column 11
(2010/06/16)
-
- (BDP)CuH: A "hot" Stryker's reagent for use in achiral conjugate reductions
-
(Chemical Equation Presented) A ligand-modified, economical version of Stryker's reagent (SR) has been developed based on a bidentate, achiral bis-phosphine. Generated in situ, "(BDP)CuH" smoothly effects conjugate reductions of a variety of unsaturated substrates, including those that are normally unreactive toward SR. Substrate-to-ligand ratios typically on the order of 1000-10000:1 can be used leading to products in high yields.
- Baker, Benjamin A.,Boskovic, Zarko V.,Lipshutz, Bruce H.
-
p. 289 - 292
(2008/09/19)
-
- Copper(I) bromide complexes from 1,2-bis(diphenylphosphano) benzene and some heterocyclic thiones
-
The synthesis, characterization and solid state emission properties of a series of mixed-ligand copper(I)bromide complexes containing 1,2-bis(diphenylphosphano)benzene (dppbz) and some heterocyclic thiones (L) are reported. The complexes are readily synthesized by the addition of the appropriate thione to a CuBr-diphosphane adduct in acetonitrile/methanol or acetone solution. The molecular structures of [CuBr(dppbz)(py2SH)], [CuBr(dppbz)(pymtH)] and [CuBr(dppbz)(imdtH2)] were established by single-crystal X-ray diffraction. Each of these structures features a tetrahedral copper(I) centre with two phosphorus atoms from the chelating diphos ligand, one bromine and the exocyclic sulfur atom of the heterocyclic thioamide unit. Slow decomposition of the mixed-ligand complexes via ligand dissociation occurs when their chloroform solutions are left to stand at room temperature for several weeks. On the basis of elemental analysis, NMR and IR spectra, the resulting coloured crystals are found to contain phosphane-free coordination polymers of composition [CuBr(L)]. At room temperature, some of the molecular complexes in the solid state exhibit strong emission assigned to a metal-ligand charge transfer of type Cu(I) → π*(PPh2).
- Kaltzoglou,Cox,Aslanidis
-
p. 3048 - 3056
(2008/10/09)
-
- 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.
- -
-
-
- Process for the preparation of lactones from higher alkenols
-
Process for the preparation of lactones, having 4 or 5 carbon atoms in the ring by reacting a higher alkenol with a carbon monoxide containing gas in the presence of a catalytic system comprising (a) a palladium compound, (b) a bidentate phosphine, arsine and/or stibine, and (c) a protonic acid having a pKa 2.
- -
-
-
- Process for the preparation of aldehydes
-
Process for the preparation of aldehydes by hydroformylation of an alkenically unsaturated compound in the presence of (a) Pd, a Pd compound, Pt and/or a Pt compound, (b) an anion of a carboxylic acid with a pKa 1 R2 -M-R-M-R3 R4, wherein M is P, As or Sb, R is a divalent organic bridging group having at least 3 carbon atoms in the bridge, and R1, R2, R3 and R4 are hydrocarbon groups.
- -
-
-
- Process for the coproduction of anilines and oxamides
-
A process for the coproduction of anilines of the formula wherein X is a halogen atom, an alkyl-, alkoxy-, aryloxy-, cyano-, ester- or trifluoromethyl group and n is an integer from 0 to 5, and oxamides of the formula wherein each R independently is an alkyl group which comprises reacting an aromatic nitro compound of the general formula wherein X and n are as defined above with carbon monoxide and a molar excess in relation to the nitro compound of an amine HNR2 wherein R is an alkyl group, in the presence of a catalyst system comprising (a) palladium metal or a compound thereof, (b) a bidentate ligand of the formula, R1R2--M--A--M--R3R4, in which M is P, As or Sb, A is a divalent organic bridging group having at least 2 carbon atoms in the bridge, none of these carbon atoms carrying substituents that may cause steric hindrance, and R1,R2,R3 and R4 represent similar or dissimilar optionally substituted hydrocarbon groups, and (c) an acid or a transition metal salt of said acid.
- -
-
-
- Palladium-Catalyzed Coupling of Aryl Halides with (Trimethylstannyl)diphenylphosphine and (Trimethylsilyl)diphenylphosphine
-
The palladium-catalyzed reaction of aryl halides with either (trimethylsilyl)diphenylphosphine or (trimethylstannyl)diphenylphosphine gives aryldiphenylphosphines in good yields, under relatively mild conditions (50-70 deg C, benzene).The reaction tolerates a number of functional groups including methyl ethers, esters, ketones, nitriles, anilides, and certain halogens.The nitro and aldehyde groups as well as compounds containing groups such as amino and hydroxyl are not tolerated.
- Tunney, S. E.,Stille, J. K.
-
p. 748 - 753
(2007/10/02)
-
- Process for the preparation of urea derivatives and catalyst system
-
The invention relates to a process for the preparation of urea derivatives of the general formula wherein R is an alkyl group and X is a halogen atom, an alkyl-, alkoxy-, aryloxy-, cyano-, ester- or trifluoromethyl group and n is from 0 to 5,which comprises reacting an aromatic nitro compound of the general formula wherein X and n are as defined above with carbon monoxide and an amine HNR2 wherein R is an alkyl group,in the presence of a catalyst system comprising (a) a group VIII noble metal or a compound thereof, (b) a bidentate ligand and (c) an acid having a pKa of more than 2 or a transition metal salt of said acid.
- -
-
-
- Synthesis of aldehydes from alcohols
-
A catalyst has been found for the low pressure hydroformylation of alcohols to produce aldehydes. This catalyst consists of a rhodium containing compound, an iodide containing compound, and a chelating Group V compound, which is used alone or in combination with a monodentate, Group V compound. It is the first rhodium-based catalyst that generates acetaldehyde via hydroformylation of the methanol. The reaction is typically carried out at 160°-180° C. and 1000-2000 psi. The acetaldehyde rate and selectivity are 1-5 Mhr-1 and 50-75%. Conventional cobalt catalysts require operating pressures of at least 3000-6000 psi in order to obtain reasonable productivities.
- -
-
-
- Carbodiphosphorane Isomers Based on a 1,3-Diphosphaindane Skeleton, and Their Precursors
-
In a search for ring-strained carbodiphosphoranes , the diastereomeric bis-phosphanes 1a(RR, SS, RS) and the symmetrical analogue 1c have been converted into the corresponding cyclic methylene-bridged bis-phosphonium bromides 2a,c and hexafluorophosphates 2b. 2a(RR;SS) and 2a(RS) were separated by fractional crystallization.Treatment of 2a-c with base (NH3 or n-BuLi) yields, in a first step, the semi-ylide salts 3a-c which, unexpectedly, undergo hydrolytic or ammonolytic cleavage at the ylidic PCHP bridge resulting in formation of the phosphane oxide or phosphane imine salts 5a, c and 6a, respectively.The second deprotonation step, using (C2H5)3P=CHCH3 as a transylidating agent, affords the conjugated bis-ylide 7a in the case of 2a, 3a(RS), but gives the carbodiphosphorane 4c in the case of the methyl-free 2c, 3c.With n-BuLi, 2a(RS) also yields the analogous species 4a(RS), probably as an Li(+) adduct, as proven by its conversion into the symmetrical methylated product 8a(RS).- 1c is methylated with CH3I at one P centre only.The resulting phosphonium salt 10 gives the mono-ylide 11 on treatment with NaNH2.
- Bowmaker, Graham A.,Herr, Rudolf,Schmidbaur, Hubert
-
p. 3567 - 3579
(2007/10/02)
-
- Carbonylvanadium, -manganese and -molybdenum Complexes of the Ligands o-C6H4EPh2(E'Ph2) (E, E' = P, As, Sb, Bi) and cis-Ph2PCH=CHPPh2
-
The photo-induced reaction between the complexes (1), η5-C5H5V(CO)4 (2), η5-C5H5Mn(CO)3 (3) or η5-C5H5Mo(CO)3CH3 (4) and the ligands o-C6H4EPh2(E'Ph2) (E = E' = P: a; E = P, E' = As: b; E = E' = As: c; E = P, E' = Sb: d; E = P, E' = Bi: e; E = As, E' = Sb: f) and cis-Ph2PCH=CHPPh2 (g), L, yields - depending on the steric requirement of L - the compounds L ( = cis-V(CO)4(-), cis-CpV(CO)2, CpMn(CO), CpMo(CO)CH3; L = a, b, c, g), L ( = V(CO)5(-), L = d; = CpV(CO)3, L = d, e; = CpMn(CO)2, L = e) or mixtures of L and L (, = V(CO)4,5, L = e, f; , = CpV(CO)2,3, L = f).In the mono-substituted species L coordination (as indicated by the 51V NMR spectra) occurs through EPh2 and E'Ph2, which is explained by a reaction path via a lable chelate 5-ring structure.Shielding of the 51V nucleus decreases in the order g > SbPh2 > PPh2 > AsPh2 > BiPh2 (derivatives of 1) and g > SbPh2 > PPh2 > BiPh2 > AsPh2 (derivatives of 2), and is smaller in the rigid chelates incorporating the o-phenylene ligands than in the more flexible structures of phospha- and arsabutane complexes.This fact is discussed in terms of hindered ?-overlap due to distortion of the EVE angle, which also results in an increase of CO valence force constants in rigid chelates. 31P coordination shifts increase according to dppe a g and arphos b (dppe = Ph2P(CH2)2PPh2, arphos = Ph2As(CH2)2PPh2). 31P NMR spectra of the molybdenum complexes suggest that the basic geometry for 4a and 4b likely is tetragonal pyramidal, while the preferred structure for 4g appears to be the trigonal bipyramid with the ligand in equatorial positions.The crystal and molecular structure of 1a is reported.The complex crystallizes in the space group C2/c (a = 2196.0, b = 1080.1, c = 2022.7 pm, β = 124.6 deg).The most striking result is the small PVP angle of 80.8 (0.2) deg.Optimized methods for the synthesis of the ligands a-f are described; the ligands are characterized by their mass spectra. - Keywords: Carbonylphosphinevanadium, Vanadium-NMR; Phosphorus-NMR
- Talay, Ridvan,Rehder, Dieter
-
p. 451 - 462
(2007/10/02)
-