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1.
Carbonylation of the palladium complexes [PdCH3(PP′)Cl] (PP′ = 1a, 1b, 1c, 1d, 1e) and [PdCH3(PP′)(CH3CN)](OTf) was investigated by means of high-pressure NMR with the determination of the half-life times t1/2. The results were rationalized on the basis of the electronic properties of the diphosphines and the nature of the solvento ligand in the first coordination sphere. The crystal structures of the complexes [Pd(1b)Cl2] and [Pd(1b)(H2O)2](OTf)2 are described (1b = 1-(diphenylphosphinomethyl)-2-[bis(3- trifluoromethylphenyl)phosphinomethyl]benzene).  相似文献   

2.
The quinolinylcyclopalladated complexes 3ab were synthesised in good yields (81% and 77%) by the insertion reaction of the prepared dinuclear palladium complexes [Pd(C,N-2-C9H4N-CHO-3-R-6)Cl(PPh3)]2 [(R = H (2a), R = OMe (2b)] with isonitrile XyNC (Xy = 2,6-Me2C6H3). The cyclopalladated complexes 3ab were also obtained in low yields (39% and 33.5%) via a one pot oxidative addition reaction of quinoline chloride 1ab with isonitrile XyNC:Pd(dba)2 (4:1). The reactions of 3ab with Tl(TfO) (TfO = triflate, CF3SO3) in the presence of H2O or EtOH causes depalladation reactions of the complexes to provide the corresponding organic compounds 4ab, 5ab and 6ab in yields (41%, 27% and 18–19%). The products were characterized by satisfactory elemental analyses and spectral studies (IR, 1H, 13C and 31P NMR). The crystal structures of 2a, 3a and 3b were determined by X-ray diffraction studies.  相似文献   

3.
The preparation and properties of mono- versus bis(carbene) Pd(II) complexes bearing unsymmetrical cyano- and ester-functionalized NHC ligands as potential IR probes were studied in detail. Direct reaction of Pd(OAc)2 with functionalized imidazolium salts afforded either bis(carbene) (3a, c) or monocarbene complexes (5, 6) with a N-coordinated imidazole co-ligand. The latter were exclusively obtained with N-ethylene substituted salts, which were found to undergo N-C cleavage reaction. The milder Ag-carbene transfer reaction on the other hand was tolerable to the length of the substituents and the nature of the functional groups. All bis(carbene) complexes (3a-c, 4a-c) were obtained as a inseparable mixture of square-planar trans-anti and trans-syn rotamers. The identity, ratio and dynamic equilibrium of these rotamers have been investigated and the relatively high rotational barrier for rotamers of 3a was estimated to be about 74 kJ mol−1 at 380 K. All eight complexes were fully characterized by NMR and IR spectroscopies, ESI mass spectrometry and X-ray single crystal and powder diffraction. A preliminary catalytic study showed that ester-functionalized complexes 4a and 4b gave rise to highly active catalyst in the double Mizoroki-Heck coupling of aryl dibromides, while the in situ ester-hydrolyzed complexes were also active in the coupling of activated aryl chlorides.  相似文献   

4.
Treatment of the thiosemicarbazones 2-XC6H4C(Me)NN(H)C(S)NHR (R = Me, X = F, a; R = Et, X = F, b; R = Me, X = Cl, c; R = Et, X = Br, d) with potassium tetrachloropalladate(II) in ethanol, lithium tetrachloropalladate(II) in methanol or palladium(II) acetate in acetic acid, as appropriate, gave the tetranuclear cyclometallated complexes [Pd{2-XC6H3C(Me)NNC(S)NHR}]4 (1a-1d). Reaction of 1a-1d with the diphosphines Ph2PCH2PPh2 (dppm), Ph2P(CH2)2PPh2 (dppe), Ph2P(CH2)3PPh2 (dppp) or trans-Ph2PCHCHPPh2 (trans-dpe) in 1:2 molar ratio gave the dinuclear cyclometallated complexes [{Pd[2-XC6H3C(Me)NNC(S)-NHR]}2(μ-diphosphine-P,P)] (2a-5a, 3b, 3d, 4c, 5c). Reaction of 1a, 1b with the short-bite or long-bite diphosphines, dppm or cis-dpe, in a 1:4 molar ratio gave the mononuclear cyclometallated complexes [Pd{2-XC6H3C(Me)NNC(S)NHR}(diphosphine-P)] (6a, 6b, 7a). The molecular structure of ligand a and of complexes 1a, 3d, 5a, 5c, 6a, 6b and 7a have been determined by X-ray diffraction analysis. The structure of complex 7a shows that the long-bite cis-bis(diphenylphosphino)ethene phosphine appears as monodentate with an uncoordinated phosphorus donor atom.  相似文献   

5.
N-Heterocyclic carbene ligands (NHC) were metalated with Pd(OAc)2 or [Ni(CH3CN)6](BF4)2 by in situ deprotonation of imidazolium salts to give the N-olefin functionalized biscarbene complexes [MX2(NHC)2] 3-7 (3: M = Pd, X = Br, NHC = 1,3-di(3-butenyl)imidazolin-2-ylidene; 4: M = Pd, X = Br, NHC = 1,3-di(4-pentenyl)imidazolin-2-ylidene; 5: M = Pd, X = I, NHC = 1,3-diallylimidazolin-2-ylidene; 6: M = Ni, X = I, NHC = 1,3-diallylimidazolin-2-ylidene; 7: M = Ni, X = I, NHC = 1-methyl-3-allylimidazolin-2-ylidene). Molecular structure determinations for 4-7 revealed that square-planar complexes with cis (5) or trans (4, 6, 7) coordination geometry at the metal center had been obtained. Reaction of nickelocene with imidazolium bromides afforded the η5-cyclopentadienyl (η5-Cp) monocarbene nickel complexes [NiBr(η5-Cp)(NHC)] 8 and 9 (8: NHC = 1-methyl-3-allylimidazolin-2-ylidene; 9: NHC = 1,3-diallylimidazolin-2-ylidene). The bromine abstraction in complexes 8 and 9 with silver tetrafluoroborate gave complexes [NiBr(η5-Cp)(η3-NHC)] 10 and 11. The X-ray structure analysis of 10 and 11 showed a trigonal-pyramidal coordination geometry at the nickel(II) center and coordination of one N-allyl substituent.  相似文献   

6.
Ferrocenyllithium reacts with M(CO)6 (M = Cr, W, Mo) in THF to give, after alkylation at oxygen, the corresponding carbene complexes 3a-c in good yield. Complexes 3a,b were characterized by X-ray analysis. These complexes react with pentylamine to give the corresponding aminocarbene complexes 7a-c and with allylamine to give, in the case of chromium and tungsten, the corresponding and expected aminonocarbene complexes 8a,b, and for molybdenum, complex 9c in which the double bond is already coordinated to the metal. 8a,b could be converted in 9a,b in excellent yield. The structure of 9a could be confirmed by an X-ray analysis. Alkylations at nitrogen could be carried on complex 9c as well as on complexes 9a,b.  相似文献   

7.
2-Phenylaniline reacted with Pd(OAc)2 in toluene at room temperature for 24 h in a one-to-one molar ratio and with the system PdCl2, NaCl and NaOAc in a 1 (2-phenylaniline):1 (PdCl2):2 (NaCl):1 (NaOAc) molar ratio in methanol at room temperature for one week to give the dinuclear cyclopalladated compounds (μ-X)2[Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}]2 [1a (X = OAc) and 1b (X = Cl)] in high yield. Moreover, the reaction between 2-phenylaniline and Pd(OAc)2 in one-to-one molar ratio in acid acetic at 60 °C for 4 h, followed by a metathesis reaction with LiBr, allowed isolation of the dinuclear cyclopalladated compound (μ-Br)2[Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}]2 (1c) in moderate yield. A parallel treatment, but using monodeuterated acetic acid (DOAc) as solvent in the cyclopalladation reaction, allowed isolation of a mixture of compounds 1c, 1cd1 [Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4](μ-Br)2[Pd{κ2-N2′,C1-2-(2′-NH2C6H4)-3-d-C6H3] and 1cd2 (μ-Br)2[Pd{κ2-N2′,C1-2-(2′-NH2C6H4)-3-d-C6H3}]2 in moderate yield and with a deuterium content of ca. 60%. 1a and 1b reacted with pyridine and PPh3 affording the mononuclear cyclopalladated compounds [Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}(X)(L)] [2a (X = OAc, L = py), 2b (X = Cl, L = py), 3a (X = OAc, L = PPh3) and 3b (X = Cl, L = PPh3)] in a yield from moderate to high. Furthermore, 1a reacted with Na(acac) · H2O to give the mononuclear cyclopalladated compound 4 [Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}(acac)] in moderate yield. 1H NMR studies in CDCl3 solution of 2a, 2b, 3a, 3b and 4 showed that 2a and 3a presented an intramolecular hydrogen bond between the acetato ligand and the amino group, and were involved in a dynamic equilibrium with water present in the CDCl3 solvent; and that the enantiomeric molecules of 2b and 4 were in a fast exchange at room temperature, while they were in a slow exchange for 2a, 3a and 3b. The X-ray crystal structures of 3b and 4 were determined. 3b crystallized in the triclinic space group with a = 9.9170(10), b = 10.4750(10), c = 12.0890(10) Å, α = 98.610(10)°, β = 94.034(10)° and γ = 99.000(10)° and 4 in the monoclinic space group P21/a with a = 11.5900(10), b = 11.2730(10), c = 12.2150(10) Å, α = 90°, β = 107.6560(10)° and γ = 90°.  相似文献   

8.
This work reports on the preparation of the complexes [PdCl2(Y1)2], [PdCl2(Y2)2] (Y1 = (p-tolyl)3PCHCOCH3 (1a); Y2 = Ph3PCHCO2CH2Ph (1b)), [Pd{CHP(C7H6)(p-tolyl)2COCH3}(μ-Cl)]2 (2a), [Pd{CHP(C6H4)Ph2CO2CH2Ph}(μ-Cl)]2 (2b), [Pd{CH{P(C7H6)(p-tolyl)2}COCH3}Cl(L)] (L = PPh3 (3a), P(p-tolyl)3 (4a)) and [Pd{CH{P(C6H4)Ph2}CO2CH2Ph}Cl(L)] (L = PPh3 (3b), P(p-tolyl)3 (4b)). Orthometallation and ylide C-coordination in complexes 2a4b are demonstrated by an X-ray diffraction study of 4a.  相似文献   

9.
The synthesis and the characterization of some new aluminum complexes with bidentate 2-pyrazol-1-yl-ethenolate ligands are described. 2-(3,5-Disubstituted pyrazol-1-yl)-1-phenylethanones, 1-PhC(O)CH2-3,5-R2C3HN2 (1a, R = Me; 1b, R = But), were prepared by solventless reaction of 3,5-dimethyl pyrazole or 3,5-di-tert-butyl pyrazole with PhC(O)CH2Br. Reaction of 1a or 1b with (R1 = Me, Et) yielded N,O-chelate alkylaluminum complexes (2a, R = R1 = Me; 2b, R = But, R1 = Me; 2c, R = Me, R1 = Et). Compound 1a was readily lithiated with LiBun in thf or toluene to give lithiated species 3. Treatment of 3 with 0.5 equiv of MeAlCl2 or AlCl3 yielded five-coordinated aluminum complexes [XAl(OC(Ph)CH{(3,5-Me2C3HN2)-1})2] (4, X = Me; 5, X = Cl). Reaction of 5 with an equiv of LiHBEt3 generated [Al(OC(Ph)CH{(3,5-Me2C3HN2)-1})3] (6). Complex 6 was also obtained by reaction of 3 with 1/3 equiv of AlCl3. Treatment of 5 with 2 equiv of AlMe3 yielded complex 2a, whereas with an equiv of AlMe3 afforded a mixture of 2a and [Me(Cl)AlOC(Ph)CH{(3,5-Me2C3HN2)-1}] (7). Compounds 1a, 1b, 2a-2c and 4-6 were characterized by elemental analyses, NMR and IR (for 1a and 1b) spectroscopy. The structures of complexes 2a and 5 were determined by single crystal X-ray diffraction techniques. Both 2a and 5 are monomeric in the solid state. The coordination geometries of the aluminum atoms are a distorted tetrahedron for 2a or a distorted trigonal bipyramid for 5.  相似文献   

10.
The syntheses and characterization of two novel ferrocene derivatives containing 3,5-diphenylpyrazole units of general formula [1-R-3,5-Ph2-(C3N2)-CH2-Fc] {Fc = (η5-C5H5)Fe(η5-C5H4) and R = H (2) or Me (3)} together with a study of their reactivity with palladium(II) and platinum(II) salts or complexes under different experimental conditions is described. These studies have allowed us to isolate and characterize trans-[Pd{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}2Cl2] (4a) and three different types of heterodimetallic complexes: cis-[M{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}Cl2(dmso)] {M = Pd (5a) or Pt (5b)}, the cyclometallated products [M{κ2-C,N-[3-(C6H4)-1-Me-5-Ph-(C3N2)]-CH2-Fc}Cl(L)] with L = PPh3 and M = Pd (6a) or Pt (6b) or L = dmso and M = Pt (8b) and the trans-isomer of [Pt{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}Cl2(dmso)] (7b). In compounds 4a, 5a, 5b and 7b, the ligand behaves as a neutral N-donor group; while in 6a, 6b and 8b it acts as a bidentate [C(sp2,phenyl),N(pyrazole)] group. A comparative study of the spectroscopic properties of the compounds, based on NMR, IR and UV-Visible experiments, is also reported.  相似文献   

11.
Sulfur analogues of the soluble guanylate cyclase (sGC) inhibitor NS2028 1a are synthesized. Treating 8-bromo-2H-benzo[b][1,4]oxazin-3(4H)-one oxime (6) with 1,1′-thiocarbonyldiimidazole (1.1 equiv) gave the carbamothioate 8-bromo-4H-[1,2,4]oxadiazolo[3,4-c][1,4]benzoxazine-1-thione (3a) in 83% yield. Alternatively reacting NS2028 1a with P2S5 (0.5 equiv) affords the carbamothioate 3a in 80% yield. Similar treatment of 8-aryl substituted NS2028 analogues 1b-d with P2S5 gave the carbamothioates 3b-d in 64-91% yields. Although quite stable, the carbamothioates 3a-d could be thermally isomerized in the presence of Cu (10 mol %) to afford the thiocarbamates 4a-d in high yields. Interestingly, in the case of carbamothioate 3a Pd and In metals also facilitated the isomerization. Furthermore, treatment of the thiocarbamates 4a-d with P2S5 (0.5 equiv) affords the carbamodithioates 5a-d in 72-89% yields. All new compounds are fully characterized including single crystal X-ray data for carbamothioate 3a and thiocarbamate 4a. Finally, a mechanism is proposed for the carbamothioate to thiocarbamate isomerization.  相似文献   

12.
The ortho-metallated complexes [Pd22(C,C)-C6H4(PPh2CHC(O)C6H5R}2(μ-Cl)2] (R = Ph (1a), NO2 (1b), Br (1c)) were prepared by refluxing equimolar mixtures of Ph3PCHC(O)C6H5R, (R = Ph, NO2, Br) and Pd(OAc)2 in MeOH, followed by an excess of NaCl. The dinuclear complexes (1a-1c) react with silver trifluoromethylsulfonate and bidentate ligands [L = bipy (2,2′-bipyridine), phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), dppp (bis(diphenylphosphino)propane)] giving the mononuclear stabilized orthopalladated complexes in endo position [Pd{κ2(C,C)-C6H4(PPh2CHC(O)R}L](OTf) [R = Ph, L = phen (2a), bipy (3a), dppe (4a), dppp (5a); R = NO2, L = phen (2b), bipy (3b), dppe (4b), dppp (5b); R = Br, L = phen (2c), bipy (3c), dppe (4c), dppp (5c); OTf = trifluoromethylsulfonate anion]. Orthometalation and ylidic C-coordination are demonstrated by an X-ray diffraction study of 2c and 3c. In the structures, the palladium atom shows a slightly distorted square-planar coordination geometry.  相似文献   

13.
The 16-electron half-sandwich complexes CpRh[E2C2(B10H10)] (E = S, 1a; Se, 1b) react with [Ru(COD)Cl2]x under different conditions to give different types of heterometallic complexes. When the reactions were carried out in THF for 24 h, the binuclear Rh/Ru complexes [CpRh(μ-Cl)2(COD)Ru][E2C2(B10H10)] (E = S, 2a; Se, 2b) bridged by two Cl atoms and the binuclear Rh/Rh complexes (CpRh)2[E2C2(B10H10)] (E = S, 3a; Se, 3b) with direct Rh-Rh bond can be isolated in moderate yields. [Ru(COD)Cl2] fragments in 2a and 2b have inserted into the Rh-E bond. If the [Ru(COD)Cl2]x was reacted with 1a in the presence of K2CO3 in methanol solution, the product [CpRh(COD)]Ru[S2C2(B10H10]] (4a), K[(μ-Cl)(μ-OCH3)Ru(COD)]4 (5a) and 3a were obtained. The B(3)-H activation in complex 4a was found. However, when the reaction between 1b and [Ru(COD)Cl2]x was carried out in excessive NaHCO3, the carborane cage opened products {CpRh[S2C2(B9H10)]}Ru(COD) (6b), {CpRh[S2C2(B9H9)]}Ru(COD)(OCH3) (7b) and 3b were obtained. All complexes were fully characterized by their IR, 1H NMR and elemental analyses. The molecular structures of 2a, 2b, 3b, 4a, 5a, and 7b have been determined by X-ray crystallography.  相似文献   

14.
Mononuclear complexes of the type, M(CO)4[Se2P(OR)2] (M = Mn, R = iPr, 1a; Et, 1b; M = Re, R = iPr, 3a; Et, 3b) can be prepared from either [-Se(Se)P(OiPr)2]2 (A) or [Se{-Se(Se)P(OEt)2}2] (B) with M(CO)5Br. O,O′-dialkyl diselenophosphate ([(RO)2PSe2]-, abbreviated as dsep) ligands generated from A and B act as a chelating ligand in these complexes. Upon refluxing in acetonitrile, these mononuclear complexes yield dinuclear complexes with a general formula of [M2(CO)6{Se2P(OR)2}2] (M = Mn, R = iPr, 2a; Et, 2b; M = Re, R = iPr, 4a; Et, 4b). Dsep ligands display a triconnective, bimetallic bonding mode in the dinuclear compounds and this kind of connective pattern has never been identified in any phosphor-1,1-diselenoato metal complexes. Compounds 2b, 3b, and 4 are structurally characterized. Compounds 2b and 3b display weak, secondary Se?Se interactions in their lattices.  相似文献   

15.
Synthetic, structural and catalysis studies of Ni(II) and Cu(II) complexes of a series of phenoxy-ketimine ligands with controlled variations of sterics, namely 2-[1-(2,6-diethylphenylimino)ethyl]phenol (1a), 2-[1-(2,6-dimethylphenylimino)ethyl]phenol (1b) and 2-[1-(2-methylphenylimino)ethyl]phenol (1c), are reported. Specifically, the ligands 1a, 1b and 1c were synthesized by the TiCl4 mediated condensation reactions of the respective anilines with o-hydroxyacetophenone in 21–23% yield. The nickel complexes, {2-[1-(2,6-diethylphenylimino)ethyl]phenoxy}2Ni(II) (2a) and {2-[1-(2,6-dimethylphenylimino)ethyl]phenoxy}2Ni(II) (2b), were synthesized by the reaction of the respective ligands 1a and 1b with Ni(OAc)2 · 4H2O in the presence of NEt3 as a base in 71–75% yield. The copper complexes, {2-[1-(2,6-diethylphenylimino)ethyl]phenoxy}2Cu(II) (3a), {2-[1-(2,6-dimethylphenylimino)ethyl]phenoxy}2Cu(II) (3b) and {2-[1-(2-methylphenylimino)ethyl]phenoxy}2Cu(II) (3c) were synthesized analogously by the reactions of the ligands 1a, 1b and 1c with Cu(OAc)2 · H2O in 70–87% yield. The molecular structures of the nickel and copper complexes 2a, 2b, 3a, 3b and 3c have been determined by X-ray diffraction studies. Structural comparisons revealed that the nickel centers in 2a and 2b are in square planar geometries while the geometry around the copper varied from being square planar in 3a and 3c to distorted square planar in 3b. The catalysis studies revealed that while the copper complexes 3a, 3b and 3c efficiently catalyze ring-opening polymerization (ROP) of l-lactide at elevated temperatures under solvent-free melt conditions, producing polylactide polymers of moderate molecular weights with narrow molecular weight distributions, the nickel counterparts 2a and 2b failed to yield the polylactide polymer.  相似文献   

16.
Synthesis, structures, and catalysis studies of gold(I) complexes of N-heterocyclic carbenes namely, a di-O-functionalized [1-(2-hydroxy-cyclohexyl)-3-(acetophenone)imidazol-2-ylidene], a mono-O-functionalized [1-(2-hydroxy-cyclohexyl)-3-(benzyl)imidazol-2-ylidene] and a non-functionalized [1,3-di-i-propyl-benzimidazol-2-ylidene], are reported. Specifically, the gold complexes, [1-(2-hydroxy-cyclohexyl)-3-(acetophenone)imidazol-2-ylidene]AuCl (1c), [1-(2-hydroxy-cyclohexyl)-3-(benzyl)imidazol-2-ylidene]AuCl (2c), and [1,3-di-i-propyl-benzimidazol-2-ylidene]AuCl (3b), were prepared from the respective silver complexes 1b, 2b, and 3a by treatment with (SMe2)AuCl in good yields following the commonly used silver carbene transfer route. The silver complexes 1b, 2b, and 3a were synthesized from the respective imidazolium halide salts by the reactions with Ag2O. The N-heterocyclic carbene precursors, 1-(2-hydroxy-cyclohexyl)-3-(acetophenone)imidazolium chloride (1a) and 1-(2-hydroxy-cyclohexyl)-3-(benzyl)imidazolium chloride (2a), were synthesized by the direct reactions of cyclohexene oxide and imidazole with chloroacetophenone and benzyl chloride respectively. The gold (1c, 2c, and 3b) and the silver (3a) complexes along with a new O-functionalized imidazolium chloride salt (1a) have been structurally characterized by X-ray diffraction. The structural studies revealed that geometries around the metal centers were almost linear in these gold and silver complexes. The gold (1c, 2c, and 3b) complexes efficiently catalyze ring-opening polymerization (ROP) of l-lactide under solvent-free melt conditions producing polylactide polymer of moderate to low molecular weights with narrow molecular weight distributions.  相似文献   

17.
Optically active ligands of type Ph2PNHR (R = (R)-CHCH3Ph, (a); (R)-CHCH3Cy, (b); (R)-CHCH3Naph, (c)) and PhP(NHR)2 (R = (R)-CHCH3Ph, (d); (R)-CHCH3Cy, (e)) with a stereogenic carbon atom in the R substituent were synthesized. Reaction with [PdCl2(COD)2] produced [PdCl2P2] (1) (P = PhP(NHCHCH3Ph)2), whose molecular structure determined by X-ray diffraction showed cis disposition for the ligands. All nitrogen atoms of amino groups adopted S configuration. The new ligands reacted with allylic dimeric palladium compound [Pd(η3-2-methylallyl)Cl]2 to gave neutral aminophosphine complexes [Pd(η3-2-methylallyl)ClP] (2a-2e) or cationic aminophosphine complexes [Pd(η3-2-methylallyl)P2]BF4 (3a-3e) in the presence of the stoichiometric amount of AgBF4. Cationic complexes [Pd(η43-2-methylallyl)(NCCH3)P]BF4 (4a-4e) were prepared in solution to be used as precursors in the catalytic hydrovinylation of styrene. 31P NMR spectroscopy showed the existence of an equilibrium between the expected cationic mixed complexes 4, the symmetrical cationic complexes [Pd(η3-2-methylallyl)P2]BF4 (3) and [Pd(η3-2-methylallyl)(NCCH3)2]BF4 (5) coming from the symmetrization reaction. The extension of the process was studied with the aminophosphines (a-e) as well as with nonchiral monodentate phosphines (PCy3 (f), PBn3 (g), PPh3 (h), PMe2Ph (i)) showing a good match between the extension of the symmetrization and the size of the phosphine ligand. We studied the influence of such equilibria in the hydrovinylation of styrene because the behaviour of catalytic precursors can be modified substantially when prepared ‘in situ’. While compounds 3 and bisacetonitrile complex 5 were not active as catalysts, the [Pd(η3-2-methylallyl)(η2-styrene)2]+ species formed in the absence of acetonitrile showed some activity in the formation of codimers and dimers. Hydrovinylation reaction between styrene and ethylene was tested using catalytic precursors solutions of [Pd(η3-2-methylallyl)LP]BF4 ionic species (L = CH3CN or styrene) showing moderate activity and good selectivity. Better activities but lower selectivities were found when L = styrene. Only in the case of the precursor containing Ph2PNHCHCH3Ph (a) ligand was some enantiodiscrimination (10%) found.  相似文献   

18.
The preparation of the new ligand 8-(di-tert-butylphosphinooxy)quinoline (1) and the palladium derivatives [PdCl2(1)] (2), [Pd(η3-all)(1)]+ [all = C3H5 (3a), 1-PhC3H4 (3b) and 1,3-Ph2C3H3 (3c)] and [Pd(η2-ol)(1)] [ol = dimethyl fumarate (4a) and fumaronitrile (4b)] is reported. The cationic species 3a-3c have been isolated as salts. The complex 3a(BF4) is obtained either from the reaction of 1 with [Pd(μ-Cl)(η3-C3H5)]2 or from the reaction of ClP(CMe3)2 with [Pd(η3-C3H5)(8-oxyquinoline)], followed in both cases by chloride abstraction with NaBF4. In the complexes, the ligand 1 is P,N chelated to the central metal, as shown by the X-ray structural analysis of 3a(BF4). At 25 °C in solution, 3a(BF4) and 3b(BF4) undergo a fast η3−η1−η3 dynamic process which brings about a syn-anti exchange only for the allylic protons cis to phosphorus, while for 4a and 4b a slow rotation of the olefin around its bond axis to palladium takes place. The complexes 2 and 3a(BF4) are efficient catalyst precursors in the coupling of the phenylboronic acid with aryl bromides and chlorides.  相似文献   

19.
A series of cationic palladium complexes of general formula [Pd(CH3)(NCCH3)(N-N)][X] (N-N = phen 1, 3-sec-butyl-1,10-phenanthroline (3-sBu-phen) 2, bpy 3, (−)-(S,S)-3,3′-(1,2-dimethylethylenedioxy)-2,2′-bipyridine (bbpy) 4, (+)-(R)-3,3′-(1-methylethylenedioxy)-2,2′-bipyridine (pbpy) 5, N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediimine (iso-DAB) 6; , OTf (OTf = triflate) b) containing different nitrogen-donor ligands were prepared from the corresponding neutral chloro derivatives [Pd(CH3)(Cl)(N-N)] (1c-6c). They were characterized by 1H NMR spectroscopy and elemental analysis. Single crystals suitable for X-ray determination were obtained for complexes [Pd(CH3)(NCCH3)(bbpy)][PF6] (4a), [Pd(CH3)(NCCH3)(iso-DAB)][PF6] (6a) and [Pd(Cl)2(bbpy)] (4c′). The latter is the result of an exchange reaction of the methyl group, present in complex 4c, with a chloride, that occurred after dissolution of 4c in CDCl3, for 1 week at 0 °C. The catalytic behavior of complexes 1a-5a and 1b-5b in the CO/styrene copolymerization was studied in CH2Cl2 and 2,2,2-trifluoroethanol (TFE) evidencing the positive effect of the fluorinated alcohol both in terms of productivity and molecular weight values of the polymers obtained. Influence of the nitrogen ligand, the anion and the reaction time in both solvents were investigated and is discussed in detail. Encouraging preliminary results were also obtained in the synthesis of polyethylene, in TFE, catalyzed by [Pd(CH3)(NCCH3)(iso-DAB)][PF6] (6a).  相似文献   

20.
Treatment of either RuHCl(CO)(PPh3)3 or MPhCl(CO)(PPh3)2 with HSiMeCl2 produces the five-coordinate dichloro(methyl)silyl complexes, M(SiMeCl2)Cl(CO)(PPh3)2 (1a, M = Ru; 1b, M = Os). 1a and 1b react readily with hydroxide ions and with ethanol to give M(SiMe[OH]2)Cl(CO)(PPh3)2 (2a, M = Ru; 2b, M = Os) and M(SiMe[OEt]2)Cl(CO)(PPh3)2 (3a, M = Ru; 3b, M = Os), respectively. 3b adds CO to form the six-coordinate complex, Os(SiMe[OEt]2)Cl(CO)2(PPh3)2 (4b) and crystal structure determinations of 3b and 4b reveal very different Os-Si distances in the five-coordinate complex (2.3196(11) Å) and in the six-coordinate complex (2.4901(8) Å). Reaction between 1a and 1b and 8-aminoquinoline results in displacement of a triphenylphosphine ligand and formation of the six-coordinate chelate complexes M(SiMeCl2)Cl(CO)(PPh3)(κ2(N,N)-NC9H6NH2-8) (5a, M = Ru; 5b, M = Os), respectively. Crystal structure determination of 5a reveals that the amino function of the chelating 8-aminoquinoline ligand is located adjacent to the reactive Si-Cl bonds of the dichloro(methyl)silyl ligand but no reaction between these functions is observed. However, 5a and 5b react readily with ethanol to give ultimately M(SiMe[OEt]2)Cl(CO)(PPh3)(κ2(N,N-NC9H6NH2-8) (6a, M = Ru; 6b, M = Os). In the case of ruthenium only, the intermediate ethanolysis product Ru(SiMeCl[OEt])Cl(CO)(PPh3)(κ2(N,N-NC9H6NH2-8) (6c) was also isolated. The crystal structure of 6c was determined. Reaction between 1b and excess 2-aminopyridine results in condensation between the Si-Cl bonds and the N-H bonds with formation of a novel tridentate “NSiN” ligand in the complex Os(κ3(Si,N,N)-SiMe[NH(2-C5H4N)]2)Cl(CO)(PPh3) (7b). Crystal structure determination of 7b shows that the “NSiN” ligand coordinates to osmium with a “facial” arrangement and with chloride trans to the silyl ligand.  相似文献   

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