Bimetallic bis(diphenylphosphino)acetylene bridged copper(I) complexes with 1,10-phenanthroline derivatives: synthesis,crystal structure,and spectroscopic characterization

A new series of bimetallic bis(diphenylphosphino)acetylene-bridged copper(I) 1,10-phenanthroline complexes, [Cu₂(dppa)₂(L)₂](BF₄)₂; L?=?1,10-phenanthroline (1); 4-methyl-1,10-phenanthroline (2); 4,7-dimethyl-1,10-phenanthroline (3); and 2,9-dimethyl-1,10-phenanthroline (4), have been prepared and characterized by spectroscopic methods. The X-ray structures of 1 and 4 were determined. The structures consist of centrosymmetric bimetallic 10-membered chair-like dimetallacycles. In 1, intermolecular C–H?π interactions result in bending of the phenanthroline ligand and sterically induced lengthening of one Cu–P bond. In 1–4, the ³¹P NMR downfield coordination shift, relative to the free ligand, correlates with the basic strength of the 1,10-phenanthroline ligands.     

New octahedral bis(diphenylphosphino)methanide derivatives and heterometallic species from mixed ligand isocyanide-dppm iron(II) complexes

The cationic [FeL(dppm)(CNPh)₃]ⁿ⁺ (1a: L = I, n = 1; 1b: L = CNPh, n = 2) are readily deprotonated by KOH to give [FeL(dppm-H)(CNPh)₃]ⁿ⁻¹ (2a and 2b). 2a reacts with [thtAuPPh₃]PF₆ to give mer-[FeI((PPh₂)₂C(H)(AuPPh₃))-(CNPh)₃]PF₆ (3). The new heterotrimetallic species [FeL((PPh₂)₂C(AuPPh₃)₂)-(CNPh)₃]ⁿ⁺ (4a and 4b) have been obtained from 1a and 1b by treatment with ClAuPPh₃ in the presence of KOH.     

Synthesis and spectroscopic characterization of tris{(diphenylphosphino) dimethylsilyl}methane complexes of cr(0) and w(0)

Treatment of M(CO)₆ (M?=?Cr, W) with (Ph₂PMe₂Si)₃CH in toluene at elevated temperatures resulted in the isolation of pale green [Cr(CO)₃{(Ph₂PMe₂Si)₃CH}] and pale brown [W(CO)₃{(Ph₂PMe₂Si)₃CH}] in high yield. These complexes have been characterized by elemental analysis, conductivity measurements, TGA, mass spectrometry, and IR, electronic, ¹H and ³¹P{¹H} NMR spectroscopy. The complexes have pseudo octahedral geometry around the metal atom with tridentate coordination of the multidentate ligand. The six-membered MPSiCSiP metallacycles are shown to have high fluxionality at room temperature on the NMR time scale.     

Synthesis and spectroscopic characterization of aryloxide derivatives of titanium(IV) and zirconium(IV)

Homo- and heteroleptic aryloxides of the type MX_4–x(OAr)_x [M = Ti^IV, Zr^IV; X = OPrⁱ, Cl; x = 1,2,3,4; OAr = OC₆H₄Prⁱ-4(OAr¹), OC₆H₃Me-2-Prⁱ-5(OAr²), OC₆H₃Me-5-Prⁱ-2(OAr³), OC₆H₂Me₃-2,4,6(OAr⁴), OC₆H₃Bu^t₂-2,4(OAr⁵), OC₆H₃Bu^t₂-2,6(OAr⁶)] have been prepared either by alkoxo–aryloxo or chloro-aryloxo exchange reactions in benzene or tetrahydrofuran. All these new derivatives have been characterized by elemental analyses, spectroscopic (i.r., ¹H-, ¹³C-n.m.r.) studies and molecular weight measurements. The FAB mass spectral studies of four representative derivatives Support a dimeric nature for [Ti(OC₆H₃Me-5-Prⁱ-2)₄], [TiCl₂(OC₆H₃Me-5-Prⁱ-2)₂], and [Zr(OC₆H₃Bu^t₂-2,4)₄(thf)], whereas the derivative [ZrCl(OC₆H₃Bu^t₂-2,4)₃(thf)] is monomeric.     

固体酸催化二氟二苯甲酮和苯胺缩合合成N-(双(4-氟苯基)亚甲基)苯胺

以固体酸为催化剂,4,4’-二氟二苯甲酮与苯胺脱水缩合,合成了N-(双(4-氟苯基)亚甲基)苯胺.比较了不同固体酸催化剂H型ZSM-5、Na型ZSM-5、介孔分子筛MCM-41(Al)及强酸型离子交换树脂Amberlyst 15的催化效果.使用比表面、NH3-TPD对催化剂进行了表征,并与催化效果关联.考察了催化剂用量、原料摩尔比、浓度及溶剂等反应条件对产物收率的影响.产物通过熔点、核磁共振谱进行了表征.结果表明,HZSM-5固体酸催化剂具有优异的催化作用.在优化条件下,以对二甲苯为反应溶剂和脱水剂,4,4’-二氟二苯甲酮0.1 mol,苯胺0.2 mol,催化剂用量2.0 g,反应24 h,产物收率达91%.此外,催化剂易于分离,能够重复使用多次.     

Gelatin/poly(aniline) composite films: Synthesis and characterization

In this work, glyoxal (Glox) - crosslinked gelatin (Gel) films have been loaded with aniline molecules, followed by their in-situ oxidative polymerization to yield Gel/poly(Ani) composite films. The films, so prepared, have been characterized by FTIR, XRD, TGA and AFM analysis. The water absorption of these films has been studied in the physiological fluid of pH 7.4 at 37°C.The dynamic water uptake data has been interpreted by various kinetic models such as power function model and Schott kinetic model. The various diffusion coefficients have also been evaluated.     

Synthesis and characterization of novel platinum group metal complexes of bis[2-(diphenylphosphino)ethyl]amine

A mixed donor tridentate ligand bis[2-(diphenylphosphino)ethyl]amine (DPEA) was synthesized in its hydrochloride form by a modified procedure and characterized by ¹H, ¹³C and ³¹P NMR spectral data. Reaction of RhCl(CO)(PPh₃)₂ with DPEA · HCl and NaBPh₄ in methanol gave the cationic Rh(I) complex [Rh(DPEA)PPh₃IBPh₄ but the reaction of IrCl(CO)(PPh₃)₂ with DPEA · HCl in boiling benzene gave a unique complex, [Ir(H)(Cl)(CO)(DPEA)]Cl, in which five different donor atoms are coordinated to the single Ir(III) ion. A neutral, RH(III) complex of the composition [RhCl₃(DPEA)] was prepared by the reaction of RhCl₃ · xH₂O with DPEA · HCl in methanol. Reaction of PdCl₂(COD) with DPEA · HCl in benzene or methanol gave the cationic complex [PdCl(DPEA)]Cl the above reaction conducted in benzene-acetone-methanol mixture gave the 1:2 complex [Pd(DPEA)₂]Cl₂. A novel trinuclear Pt(II) complex of the composition [Pt₃Cl₃(DPEA)₃]Cl₃ was prepared by the reaction of K₂PtCl₄ and DPEA · HCl in water-acetone mixture. Reaction of K₂PtCl₄, DPEA · HCl and NH₄PF₆ in water ethanol mixture gave the binuclear, cationic complex, [Pt₂(DPEA)₃](PF₆)₄. All the complexes were characterized by elemental analysis, conductivity, ¹H and ³¹P NMR spectral data.     

Synthesis and Structure of Di［bis（diphenylphosphino）ethane］ Copper（Ⅱ） Dinitrate

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Synthesis and characterization of bis(cyclopentadienyl)bis(hexafluoroantimonato) titanium(IV)

Reaction of titanocene dichloride with two equivalents of silver hexafluoroantimonate in sulphur dioxide quantitatively yields Cp₂Ti(SbF₆)₂ (Cp = η⁵-C₅H₅) and AgCl. The titanocene bishexafluoroantimonate was recrystallized from SO₂ and characterized by chemical analysis, ¹H NMR, IR and mass spectroscopy.     

Synthesis and characterization of bis(methoxyl hydroxyl)-functionalized disiloxane and polysiloxane oligomers derivatives therefrom

With purpose to prepare waterborne polyurethane with improved performance, bis(methyoxyl hydroxyl)-functionalized polysiloxanes with different dimethylsiloxane segment length were prepared. The preparation includes three steps, the first is synthesis of 1,3-bis(glycidoxypropyl)tetramethyldisiloxane (compound I) via hydrosilylation of allylglycidyl ether with tetramethyldisiloxane, followed by a subsequent methoxylation of the resultant compound from the hydrosilylation to give 1,3-bis(3-(1-methoxy-2-hydroxypropoxy)propyl)tetramethyldisiloxane (compound II). Using this compound II and octamethylcyclotetrasiloxane (D₄), an equilibrium reaction was carried out to obtain the target Product III, i.e. bis(methoxyl hydroxyl)-functionalized polysiloxanes. The ratio of D₄/compound II was varied in order to prepare product III with different segment length consisting of dimethylsiloxane units. At each step, the outcome compounds were characterized through Infrared, ¹H NMR, ¹³C NMR as well as H-H and H-C Correlated Spectroscopy (COSY). The results showed that each step was successfully carried out and objective products were achieved. It was estimated that compound II was not exclusive in the methoxylation step. Characterizations of the compound II enabled us to give a reliable quantitative amount for the by-products for the first time. In addition, the molecular weights of the final product III with varying dimethylsiloxane length were estimated by hydroxyl group analysis, ¹H NMR and GPC, which showed a good agreement between the theoretical molecular weights and those from these tests.     

Synthesis and characterization of bis(2-aminophenyl)disulphide diimine derivatives and their ruthenium complexes

Condensation of bis(2-aminophenyl)disulphide with aromatic aldehydes yielded the corresponding dithiophenyldiimines. Dinuclear ruthenium complexes were obtained by reacting the diimines (3) [bis(3-nitrobenzaldehyde)-phenyldisulphide diimine], (5) [bis(2-chlorobenzaldehyde)-phenyldisulphide diimine], (8) [bis(2-methoxybenzaldehyde)-phenyldisulphide diimine] and (9) [bis(2-hydroxybenzaldehyde)-phenyldisulphide diimine], with RuCl₃ in the presence of L (L=2,2-bipyridine, 1,10-phenanthroline, 3,4-diaminotoluene, pyridine and PPh₃) in EtOH. The two metal centres, connected through bridging chlorides, are in octahedral environments with one metal centre coordinated to sulphur and water while the other is coordinated to L.     

Synthesis and spectroscopic characterization of new organotin(IV) complexes with bis(3,5-dimethylpyrazol-1-yl)dithioacetate

New organotin(IV) derivatives containing the anionic ligand bis(3,5-dimethylpyrazolyl)dithioacetate [L₂CS₂]^? have been synthesized by reaction of SnR _n X_{4? n} (R?=?Me, Ph, ⁿ Bu or Cy; n?=?1–3) acceptors and Li[L₂CS₂]. Mononuclear complexes of the type [L₂CS₂]R _n SnCl_{4? n ?1}} have been obtained and fully characterized by elemental analyses and FT-IR in the solid state, and by NMR (¹H and ¹¹⁹Sn) spectroscopy, conductivity measurements and electrospray ionization mass spectrometry (ESI-MS) in solution. ESI-MS spectra of methanol solutions of diorganotin derivatives, recorded with fragmentor potentials of 0, 50, 100 and 150?V, show the occurrence at 150?V of peaks attributable to the loss of the CS₂ group from the ligands and the formation of stable tetraorganodistannoxane species.     

Synthesis and characterization of sodium bis(trimethylstannyl) amide and bis(trimethylsilyl) bis(trimethylstannyl) -phospha-tetrazene

Sodium bis(trimethylstannyl)amide NaN(SnMe₃)₂, isolated by the reaction of trimethylstannyldiethylamine with sodium amide, reacts with tris(trimethylsilyl)hydrazino—dichloro-phosphine to form bis(trimethylsilyl)bis(trimethylstannyl)-2-phospha-2-tetrazene, (Me₃Si)₂N-N=P-N(SnMe₃)₂. Both the molecules have been isolated and characterized.     

Synthesis and properties of bis(pyridylmethylene)mercury derivatives

The action of ammonia on - and -monomercurimethylenePyrylium perchlorates gave bis(pyridylmethylene)mercury derivatives, which undergo decomposition to the corresponding pyridine derivatives and mercuric chloride.See [1] for our preceding communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 887–888, July, 1981.     

Synthesis and characterisation of linked triosmium clusters using the bis(diphenylphosphino)acetylene ligand

The reaction of Os₃(CO)₁₁(NCMe) with bis(diphenylphosphino)acetylene (dppa) at room temperature affords [Os₃(CO)₁₁]₂(dppa) (1) in good yield, while Os₃(CO)₁₀(NCMe)₂ with an excess of dppa gives [Os₃(CO)₁₀(dppa)]₃ (2) and [Os₃(CO)₁₀(dppa)]₄ (3) in moderate yields. The structure of 1 has been determined by a single crystal X-ray diffraction study.