18399-62-7Relevant academic research and scientific papers
Phosphorus-Carbon Bond Forming Reactions of Diphenylphosphenium and Diphenylphosphine Triflate Complexes of Tungsten
Jayaraman, Arumugam,Sterenberg, Brian T.
, p. 2367 - 2377 (2016/08/02)
The complex [W(CO)5{PClPh2}] reacts with AlCl3 to form a mixture of the phosphenium complex [W(CO)5{PPh2}][AlCl4] and an isocarbonyl, with GaCl3 to form [W(CO)5{PPh2}][GaCl4], and with silver trifluoromethanesulfonate to form [W(CO)5{P(OSO2CF3)Ph2}]. All three complexes react as strong P electrophiles, undergoing electrophilic substitution reactions with aromatic and heteroaromatic compounds, alkenes, and alkynes, to form aromatic and heteroaromatic phosphines, allyl phosphines, and alkynyl phosphines, respectively. Alkenes lacking cleavable γ-H atoms and internal alkynes undergo tandem electrophilic addition/substitution reactions, adding between the P and one of the phenyl rings to form fused P heterocycles. The newly formed phosphines can be removed from the tungsten complex by photolysis in the presence of bis(diphenylphosphino)ethane.
Insertion of phosphinidene complexes into the P-H bond of secondary phosphine oxides: A new version of the phospha-Wittig synthesis of P=C double bonds
Hao, Yanwei,Wu, Di,Tian, Rongqiang,Duan, Zheng,Mathey, Fran?ois
, p. 891 - 893 (2016/01/15)
Terminal phosphinidene complexes [RP-W(CO)5], as generated at 60 °C in the presence of copper chloride from the appropriate 7-phosphanorbornadiene complexes, react with secondary phosphine oxides Ar2P(O)H to give the insertion products into the P-H bonds. After metalation with NaH, these products react with aldehydes to give the corresponding phosphaalkenes which are trapped by dimethylbutadiene.
α-Phosphanyl amino acids: Synthesis, structure and properties of alkyl and heterocyclic N-substituted diphenylphosphanylglycines Dedicated to Professor Dr. Dr. h.c. Manfred Scheer on the occasion of his 60th birthday
Lach, Joanna,Peulecke, Normen,Kindermann, Markus K.,Palm, Gottfried J.,K?ckerling, Martin,Heinicke, Joachim W.
, p. 4933 - 4945 (2015/06/23)
N-Alkyl and N-heterocyclic substituted diphenylphosphanylglycines 1a-j were synthesized by a convenient one-pot, three-component reaction of diphenylphosphane, the corresponding primary amine and glyoxylic acid hydrate in diethyl ether. Phosphanylglycolates 2 and phosphoniobis(glycolates) 3 were detected as intermediates. In the case of steric hindrance or low basicity of the amine only 2 or mixtures of 2 and 1 are formed. Reactivity studies of selected phosphanylglycines showed facile decarboxylation and hydrolysis, oxidation and formation of coordination compounds with BH3 or W(CO)5. N-Alkyl derivatives (tert-butyl, n-hexyl, benzhydryl) with moderate steric hindrance reacted with Ni(COD)2 in THF or toluene in the presence of ethylene with heating under pressure to yield highly active oligomerization catalysts, and converting the ethylene to liquid and low-molecular-weight solid ethylene oligomers (MNMR 500-1250 g/mol) with high selectivity for linear α-olefins. Smaller N-alkyl or N-heterocyclic amino substituents at the phosphanyl acetic skeleton interfere with the ethylene conversion and deactivate the catalyst. The structures of the compounds were elucidated by solution NMR and single crystal XRD studies.
Mechanism of phosphinidene complex arylation by arylboronic acids
Ng, Yong Xiang,Mathey, Francois
, p. 1322 - 1324 (2014/04/03)
The arylation reaction of terminal phosphinidene complexes [RP-W(CO) 5] by arylboronic acids is very sensitive to steric hindrance and the electronic properties of the substituents on the aryl ring. On the basis of DFT calculations and addition
Syntheses, Reactivities and Molecular Structures of Tungsten Complexes containing the Diphenylphosphinodithioformato Ligand
Yih, Kuang-Hway,Lin, Ying-Chih,Cheng, Ming-Chu,Wang, Yu
, p. 1305 - 1314 (2007/10/02)
Treatment of 1 with CS2 afforded 3 which was also synthesized from the reaction of with 2.The reactions of 3 with various alkyl halides gave the neutral complexes , and the reactions of 3 with acyl halides gave > (R = Me or Ph).Both alkylation and acylation reactions occur at the sulfur atom.Treatment of 3 with afforded in which the two metal atoms were bridged by the PPh2CS2(1-) ligand.The reaction of 3 with (pip = piperidine) yielded and the dithiocarbamato tungsten complex .Complex 3 reacted with organic α,ω-diiodides (CH2I2, C2H4I2, C3H6I2), giving the phosphine bridged dinuclear complexes 2(μ-CH2)n> (n = 1-3), and only in the reaction of C3H6I2, was a mononuclear complex >> seen as a minor product.Complex 2(CO)2> was obtained from the reaction of 3 with oxalyl bromide in CH2Cl2.Thermolysis of 3 in tetrahydrofuran (thf) gave an anionic product identified as .All of the complexes were identified by spectroscopic methods.The structures of complexes 2, 3 and 4a were confirmed by single-crystal X-ray diffraction analyses.Crystal data: 2, monoclinic, space group P21, a = 10.244(4), b = 9.877(4), c = 11.124(3) Angstroem, β = 102.02(2) deg, Z = 2, R = 0.062, R' = 0.073 based on 1180 reflections with I > 2 ?(I); 3, triclinic, space group P, a = 10.688(3), b = 11.070(2), c = 12.785(2) Angstroem, α = 88.26(1), β = 81.87(2), γ = 74.081(17) deg, Z = 2, R = 0.028, R' = 0.025 based on 4557 reflections with I > 2?(I); 4a, triclinic, space group P, a = 9.177(5), b = 9.403(3), c = 12.461(6) Angstroem, α = 90.00(3), β = 103.85(4), γ = 94.79(3) deg, Z = 2, R = 0.041, R' = 0.041 based on 2442 reflections with I > 2?(I).
Studies of CO labilization and intramolecular hydride transfer reactions in group VI (Cr, Mo, W) metal-platinum heterobimetallic μ-phosphido hydrido carbonyl complexes
Powell, John,Gregg, Michael R.,Sawyer, Jeffery F.
, p. 4451 - 4460 (2008/10/08)
Oxidative addition of the P-H bond of the secondary phosphine complexes M(CO)5(PR2H) (M = Cr, Mo, W; R = Ph, nPr) to Pt(C2H4)(PPh3)2 gives (OC)5M(μ-PR2)PtH(PPh3)2, which rapidly loses CO (a reversible process) to give (OC)4M(μ-PR2)(μ-H)Pt(PPh3)2 via a "platinum-assisted mechanism" involving PPh3 dissociation, formation of a μ-carbonyl intermediate (OC)4M-(μ-PR2)(μ-CO)PtH(PPh3), subsequent rearrangement to (OC)4M(μ-PR2)(μ-H)Pt(CO)(PPh3), and substitutional loss of CO from Pt (by PPh3). The complexes (OC)4M(μ-PPh2)(μ-H)Pt(PR3)2 (PR3 = PEt3, PMe2Ph) can be obtained from the reaction of M(CO)5(PPh2Li) and trans-PtHCl(PR3)2. Reaction of M(CO)5(PPh2H) with Pt(1,5-COD)2 in the presence of ethylene gives (OC)5M(μ-PPh2)PtH(COD), which rapidly rearranges, via β-H transfer, to the complex (OC)4M(μ-PPh2)(μ-CO)Pt(η 3-cyclooctenyl). Addition of M(CO)5(PPh2H) to Pt(C2H4)2(PCy3) gives the complexes (OC)4M(μ-PPh2)(μ-H)Pt(CO)(PCy3) while reaction of cis-(OC)4M(PEt3)(PPh2H) (M = Mo, W) with Pt(C2H4)2(PCy3) gives mer-(OC)3(PEt3)M(μ-PPh 2)(μ-CO)PtH(PCy3). For M = Mo this μ-carbonyl terminal-hydrido complex equilibrates with a small amount of the μ-hydrido terminal-carbonyl isomer fac-(OC)3(PEt3)Mo(μ-PPh 2)(μ-H)Pt(CO)(PCy3). The molecular structure of the complexes (OC)4Cr(μ-PPh2)(μ-H)Pt(PEt3)2 and (OC)4Cr(μ-PPh2)(μ-CO)Pt(η 3-cyclooctenyl) (contains a semibridging carbonyl ligand) have been determined by single-crystal X-ray diffraction methods. The complex (OC)4Cr(μ-PPh2)(μ-H)Pt(PEt3)2 crystallizes in the space group Cc with a = 16.719 (9) A?, b = 11.468 (3) A?, c = 18.275 (6) A?, β = 113.68 (3)°, V = 3209 A?3, and Z = 4. The structure was refined to R = 0.0346 and Rw = 0.0401 for the 3801 reflections with I > 3σ(I). Corresponding data for (OC)4Cr(μ-PPh2)(μ-CO)Pt(η 3-cyclooctenyl) are space group P21/a, a = 25.212 (3) A?, b = 10.172 (2) A?, c = 9.577 (2) A?, β = 90.53 (1)°, V = 2456 A?3, and Z = 4. R = 0.0329, Rw = 0.0382 for 3384 reflections with I > 3σ(I).
Reactions Leading to Formation and Cleavage of Metal-Metal and Metal-μ-Phosphido Bonds in Binuclear Molybdenum and Tungsten Complexes. Structural Analyses of W2(CO)8(μ-PPh2)2 and Its Two-Electron Reduction Product, 2
Shyu, Shin-Guang,Calligaris, Mario,Nardin, Giorgio,Wojcicki, Andrew
, p. 3617 - 3625 (2007/10/02)
Reduction of M2(CO)8(μ-PPh2)2 (M= Mo (1-Mo) or W (1-W)) and reactions of various binuclear molybdenumand tungsten anionic products were found generally to proceed with a remarkably facile scission or formation of M-M and M-(μ-PPh2) bonds.Thus, complexes 1 are converted by M'BR3H (M'= Li, R= Et; M'= K, R= sec-Bu) or LiAlH4 in THF to the M-M bond cleaved 2- (2) or to (3) depending on the nature and, usually the amount of the reductant.Reactions of 1 with LiR (R= Me (a), N-B (b), Ph (c)) afford the acyl anions (4a-c), of which yield the carbene complexes (5a,c) when treated with Me3OBF4.The M-M bond of 3 is readily broken by CO and n-BuLi to give - (6) and 2, respectively.Treatment of 3 with CF3COOH leads to a fragmentation of the binuclear unit with the formation of cis-M(CO)4(PPh2H)2 and M(CO)5(PPh2H).The dianions 2 are converted to the M-M bonded 3 and 4a when reacted with 1 equiv of CF3COOH and MeI (in THF or DMF), respectively.Possible mechanisms of these reactions are discussed.The structures of 1-W and its 2-electron reduction product,Li(THF)3+>22-W, were determined by single-crystal X-ray diffraction analyses.Both crystals are monoclinic of space group P21/c, with a= 9.830 (2) Angstroem, b= 19.802 (4) Angstroem, c= 16.889 (5) Angstroem, β= 103.72 deg, and Z= 4 for 1-W and a= 11.265 (5) Angstroem, b= 19.546 (3) Angstroem, c= 16.446 (5) Angstroem, β= 122.07 (3) deg, and Z= 2 for +>22-W.The structure of 1-W was solved and refined to R= 0.030 and RW= 0.33 by using 5206 independent reflections, whereas the structure of +>22-W was solved and refined to R= 0.051 and RW= 0.062 by using 3987 independent reflections.Both structures possess a planar W2P2 core.The W-W distance of 3.0256 (4) Angstroem in 1-W increases to a nonbonding value of 4.1018 (4) Angstroem in 2-W, and the W-P-W bond angles of 75.14 deg (mean) in 1-W widen to 104.20 deg in 2-W.The Li+ ion in +>22-W possesses an almost regular tetrahedral oxygen environment, being attached to three THF molecules and an equatorial CO of 2-W.
Reactions of M2(CO)8(μ-PPh2)2 (M = Mo or W) with BR3H- and LIR nucleophiles. Proton-induced cleavage of M-(μ-PPh2) bonds in binuclear anionic complexes
Shyu, Shin-Guang,Wojcicki, Andrew
, p. 809 - 812 (2008/10/08)
Reactions of M2(CO)8(μ-PPh2)2 (2, M = Mo or W) with 1 equiv of M′BR3H (M′ = Li or K; R = Et or sec-Bu) in THF proceed to [(CO)4M(μ-PPh2)M(CO)4-Scheme I (Chemical Equation Presented) (PPh2H)]- (3) and with 2 equiv of M′BR3H or LiAlH4, to [M2(CO)8(μ-PPh2)2]2- (4). Treatment of 4 with 1 equiv of CF3COOH in THF affords 3, whereas treatment of 3 with 1 equiv of CF3COOH yields cis -M(CO)4(PPh2H)2 and M-(CO)5(PPh2H) as major and minor products, respectively. Reactions of 2 with LiR (R = Me, n-Bu, and Ph) proceed regiospecifically to the equatorial isomers of [M2(CO)7-(COR)(μ-PPh2)2] -, which are alkylated by Me3O+BF4- to yield M2(CO)7[C(OMe)R] (μ-PPh2)2 (R = Me).
The reaction chemistry of transition-metal diphenylphosphorus complexes with organoaluminum compounds. The synthesis, characterization, and crystal and molecular structure of Cr(CO)5[PPh2(CH2)4OAl(CH 2SiMe3)2], an example of THF cleavage
Tessier-Youngs,Youngs, Wiley J.,Beachley Jr.,Churchill, Melvyn Rowen
, p. 1128 - 1138 (2008/10/08)
Metathetical and small molecule elimination reactions between appropriate transition-metal carbonyl diphenylphosphorus complexes and organoaluminum compounds have been investigated as synthetic routes to transition-metal derivatives of amphoteric ligands. The synthesis, characterization, and properties of the starting compounds for the metathetical reactions M(CO)5PPh2K·n(dioxane) (M = Cr, W, n = 2; M = Mo, n = 1) from M(CO)5PPh2H and KH are described. All data confirm that the dioxane molecules in these complexes retain their identity as cyclic ethers. Subsequent reactions of Cr(CO)5PPh2K·2(dioxane) with AlR2Br (R = Br, Me, Et, CH2SiMe3) in THF lead to the formation of high yields of fully characterized compounds with the empirical formula Cr(CO)5[PPh2(CH2)4OAlR2]. The (CH2)4O unit arises from the cleavage of the THF molecule. No THF-aluminum adducts are observed. The compound Cr(CO)5-[PPh2(CH2)4OAl(CH 2SiMe3)2] which incorporates a new amphoteric ligand has also been characterized by an X-ray structural study. The crystal is composed of dimeric units of formula [Cr(CO)5[PPh2-(CH2)4OAl(CH 2SiMe3)2]]2 which are in the centrosymmetric monoclinic space group P21/n with a = 11.939 (3) A?, b = 14.940 (A?), c = 21.014 (5) A?, β= 102.88 (2)°, V = 3654 A?3, Z = 2 (dimeric units), and mol wt 1301.5. Diffraction data (20(max) = 35°, Mo Kα radiation) were collected with a Syntex P21 automated four-circle diffractometer, the structure was solved by Patterson and difference-Fourier techniques, and the model was refined to RF = 9.2% and RwF = 8.2% for 1515 reflections with |Fo| > 3σ(|Fo|). The dimeric molecule lies on an inversion center. Each octahedral (OC)5CrPPh2- fragment is linked by an -(CH2)4O-unit (formed by cleavage of THF) to the two Al(CH2SiMe3)2 fragments. The central Al-O-Al-O ring is strictly planar, with obtuse Al-O-Al angles of 100.3 (6)° and acute O-Al-O angles of 79.7 (5)°. The second route to chromium derivatives of amphoteric aluminum-phosphorus ligands, small molecule elimination reactions between Cr(CO)5PPh2H and AlMe3 or AlMe2H, does not lead to compounds with Cr-P-Al bonds. Our observations suggest that the major site of reaction for the aluminum compounds is the carbonyl ligand.
