Diphenyl Phosphino Research Articles

Structural characterization, electronic and photophysical properties of phosphane-based copper(I) complexes and their application to cyan LEDs

Two dinuclear Cu(I) complexes, [Cu2(dppe)(dppbz)2I2](1) and [Cu2(dppb)(dppbz)2I2] (2) (dppe = 1, 2-bis(diphenylphosphino)ethane, dppb = 1,4-bis(diphenylphosphino)butane, dppbz = 1,2-bis (diphe nylphosphino)benzene), have been prepared and characterized by IR, TG, XRD, elemental analysis and X-ray crystal structure analysis. Structural analysis indicates that diphosphane ligands connect two Cu atoms to form the S-shape configurations in complexes 1 and 2. DFT calculations demonstrate that the HOMO → LUMO energy gap and Mülliken atomic charges for 1 and 2 are affected by increasing the alkyl chain length of diphosphane ligands, but the composition of HOMOs and LUMOs are hardly changed at the different alkyl chain length of diphosphane ligands. The solid-state luminescent properties of complexes 1 and 2 are observed at 77 K and 298 K, showing that the maximum emission lifetime and quantum yields respectively approach to 6 μs and 26 % at 298 K. Moreover, dinuclear Cu(I) complexes are used to fabricate the cyan light-emitting diodes with the maximum EQE of ca. 20 %.

Synthesis, structures, DFT studies and properties of novel tertiary diphosphines based on α- and β-naphthylamine

Based on α- and β-naphthylamine, two new diphosphines, N,N-bis((diphenylphos phino)methyl)naphthalen-1-amine (1) and N,N-bis((diphenylphosphino)methyl)naphthalene -2-amine (2), have been prepared and characterized by IR, 1H NMR, 31P NMR, TG, UV-Vis, XRD and X-ray crystal structure analysis. Structural analysis shows that the two Ph2PCH2- groups in 1 and 2 are disposed in an anti configuration, and the change of the position of the (Ph2PCH2)2N-group on the naphthalene moiety results in different spatial configurations of the two Ph2P- groups and different weak interactions, such as C-H…π and π–π interactions. DFT studies show that the composition of the HOMOs for 1 and 2 are almost the same (the naphthyl group with admixed N and P atoms), but the ingredients of the LUMOs for 1 are different from that for 2, coinciding with the change of Mülliken atomic charges. Moreover, the emission spectra show that the emissions of complexes 1 and 2 in acetonitrile solution are not similar to those of solid-state samples.

Structures, electronic and luminescent properties of Cu(I)-quinoline complex at different temperatures and its application to red light-emitting diode

A mononuclear Cu(I) complex, Cu(dppb)(2,2′-biquinoline)]BF4(1) (dppb = 1, 2-bis(diphenyl phosphino)benzene), has been synthesized and characterized at 100 K, 150 K, 200 K, 250 K and 298 K. The structural analysis reveals that the rise of temperature from 100 K to 298 K leads to the increasement of molecular size, such as the unit-cell parameters and volume, and the change of bond lengths, bond angles, CH…π and π…π interactions. DFT calculations indicate that the HOMO → LUMO energy gap and Mülliken atomic charges are changed by the increase of temperature from 100 K to 298 K, and the component of the HOMOs and LUMOs are barely changed at 100–298 K, which is in accordance with the variation of DOS and PDOS at different temperatures. Meanwhile, the surprising broad blue-yellow excitation bands are observed at 100–298 K and the maximum emission is increasing with the blue shift from 735 nm at 100 K to 685 nm at 298 K. Furthermore, the emission decay time of complex 1 reaches 3 μs at 298 K. In addition, copper(I) complex 1 is used to fabricate the monochromatic LED, which emits a red light.

POLYMERIZATION OF METHYL METHACRYLATE IN PRESENCE OF INITIATING SYSTEMS BASED ON IRON COMPLEXES OF VARIOUS STRUCTURES

The features of the radical polymeriation of methyl methacrylate using initiating systems based on benzoyl peroxide and iron complexes with various ligand environments, including ferrocenes containing electron-donating and electron-withdrawing substituents in cyclopentadienyl rings, as well as cyclopentadienyl carbonyl-containing derivatives of iron, have been studied. The influence of the structure of iron complexes on the kinetics of the radical polymerization of methimethacrylate, as well as the molecular weight characteristics of the synthesized polymers, was estimated. It was established that, according to the effect on the methylmethacrylate polymerization rate in the presence of the initiating systems under study, the metal complexes are arranged in the series: 1,1'-dibromoferrocene, bromo (η5-cyclopentadienyl)dicarbonyl iron>1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino- ferrocene)>ferrocene>1-di-tert-butylphosphinoferrocene>1,1-bis-di-tert-butyl-phosphino-ferrocene> bis (η5-cyclopentadienyl) dicarbonyl iron>1–bromo-1′- diphenyl phosphino ferrocene>1-diphenylphosphino-1'-di-tert-butylphosphinoferrocene. Polymers based on polymethylmethacrylate synthesized in the presence of the studied cyclopentadienyl complexes of iron and benzoyl peroxide are capable of acting as macroinitiators in postpolymerization processes. In particular, it was found that polymethylmethacrylate synthesized with the participation of 1,1′-dibromoferrocene and bromo (η5-cyclopentadienyl) dicarbonyl iron in the presence of a peroxide initiator allows the synthesis of postpolymers. Using NMR spectroscopy, it was found that methyl methacrylate-based polymers synthesized both in the presence of the above iron complexes and its analogs obtained by traditional radical polymerization have an atactic structure. Using differential scanning calorimetry, it was shown that methyl methacrylate-based polymers obtained in the presence of cyclopentadienyl and carbonyl iron complexes have a higher glass transition temperature compared to similar polymers synthesized by radical polymerization involving only the peroxide initiator. The temperature of the onset of decomposition of these polymers remains almost unchanged.

Thermally activated delayed fluorescence of copper(I) complexes using N, N′-heteroaromatic of 2-(5-phenyl-1,2,3- triazole)pyridine as ligand

Two Cu(I) complexes of [Cu(PPh3)2(pptz)]BF4 and [Cu(POP)(pptz)]BF4 using 2-(5-phenyl-1,2,3-three triazole)pyridine (pptzH), triphenyl phosphine (pph3) and (bis-[2-(diphenyl phosphino) phenyl]ether) (POP) as ligands were synthesized and characterized. The complexes [Cu(PPh3)2(pptz)]BF4 and [Cu(POP)(pptz)]BF4 exhibit thermally activated delayed fluorescence (TADF) features with photoluminescence quantum yields (ϕPL) of 89.87% and 27.82% at room temperature in solid state. The maximum emission peak of [Cu(PPh3)2(pptz)]BF4 is located at 490 nm. The solution-processing organic-light emitting devices (OLEDs) were fabricated by using [Cu(PPh3)2(pptz)]BF4 and [Cu(POP)(pptz)]BF4 as emitters and 4,4′,4′′-tris(N-carbazolyl)-triphenylamine (TCTA) as host. The device based [Cu(POP)(pptz)]BF4 displayed the better electroluminescent performance with the maximum current efficiency of 2.1 cd/A than that of device used [Cu(PPh3)2(pptz)]BF4 as emitter.

Chiroptical Activity in BINAP- and DIOP-Stabilized Octa- and Undecagold Clusters

In order to learn more about the origin of chirality in chiral organometallic complexes and to contribute to the understanding of the differences in chiroptical activity of metal clusters stabilized by various phosphine ligands, we examined the optical properties of undecagold (Au113+) and octagold (Au82+) clusters protected by two types of bisphosphine ligands [BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) and DIOP (o-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane)]. The chirality of pairs of clusters [Au11(BINAP)4Cl2]+, [Au11(DIOP)4Cl2]+ and [Au8(BINAP)3(PPh3)2]2+, [Au8(DIOP)3(PPh3)2]2+ are investigated with density functional theory (DFT) and time–dependent density functional theory (TDDFT). The geometries of the octa- and undecagold cores in the model clusters are similar to the gold cores of the crystal structures. Theoretical optical absorption and CD spectra of the model clusters are in good agreement with experimental data. Three main hypotheses to explain the different chirop...

Catalytic property of [FeFe]-hydrogenase model complex: [(μ-dmedt)Fe2(CO)5](μ-DPPF-O) (DPPF = 1,1′-bis(diphenylphosph ino)ferrocene) for the selective phenol hydroxylation

A novel [FeFe]-hydrogenase biomimetic catalyst [(μ-dmedt)Fe2(CO)5](μ-DPPF-O) (1) was prepared by CO-substitution in the (μ-dmedt)[Fe2(CO)6] complex with DPPF in THF. Confirmation of the catalyst structure was determined by FTIR, 1H NMR, 13C NMR, 31P NMR and single crystal X-ray diffraction. Complex 1 exhibited better catalytic reactivity for phenol hydroxylation than the all-carbonyl complex (μ-dmedt)[Fe2(CO)6]. The dihydroxybenzene selectivity of 94.0% and phenol conversion of 42.9% were obtained under the optimal reaction conditions. The relationships between electron density of the FeFe bond and the catalytic activity of these complexes were revealed, which showed that the more electron rich the FeFe bond is, the better catalytic hydroxylation activity was achieved.

Thickness dependence of structural and optical properties of novel 2-((1, 1-bis(diphenylphosphino)-2-phenylpropan-2-yl)-chromium tetracarbonyl-amino)-3-phenylpropanoic acid copper (II) (DPP-Cr-Palan-Cu) nanocrystalline thin film

A novel transition metal complex and its derivatives, 2-((1,1-bis(diphenyl phosphino)-2-phenylpropan-2-yl)-chromium tetracarbonyl-amino)-3-phenylpropanoic acid copper (II) (DPP-Cr-Palan-Cu) were synthesized. X-ray diffraction showed the existence of the nanostructure of the as-deposited DPP-Cr-Palan-Cu thin films. Also, The XRD for DPP-Cr-Palan complex in a powder form was of a polycrystalline nature and of a monoclinic crystal system with space group Trigonal/P3. The optical properties of DPP-Cr-Palan-Cu thin films are prepared by thermal evaporation technique at room temperature were investigated. Optical properties were studied for the DPP-Cr-Palan-Cu thin films with various thickness 100, 150, 200 and 250nm at normal incidence of light in the wavelength range of 300–850nm. The refractive index (n) and the absorption index (k) were computed using the obtained data of transmittance T(λ) and reflectance R(λ). The complex dielectric constant, optical conductivity, optical band gap Egopt, volume energy loss (VELF), and surface energy loss (SELF) functions were calculated and interpreted. The results of the optical absorption data showed that DPP-Cr-Palan-Cu thin films have mainly direct energy gap bands in the energy range from 1.924 to 1.662eV for film thickness 100nm to 250nm, respectively. The obtained results indicate that the DPP-Cr-Palan-Cu organic semiconductor thin film is a good candidate in optoelectronic devices based on its band gap and dispersion parameters.

Synthesis, structure, and spectroscopic properties of Cu+ complexes and its application to solar cells

A series of Cu+ complexes, [Cu2(L)(dppe)2](BF4)2 (1), [Cu2(L)(dppp)2](BF4)2·2CH3CN (2), and [Cu2(L)(dppe)2](ClO4)2 (3) (L = N,N′-bis(dipyridin-2-ylmethylene)benzene-1,4-diamine, dppe = 1,2-bis(diphenylphosphino)ethane, and dppp = 1,3-bis(diphenyl phosphino)propane), have been synthesized and characterized by IR, 1H NMR, 31P NMR, UV–vis spectrum, and X-ray crystal structure analysis. The structural analysis reveals each Cu+ is four-coordinate N2P2 and adopts a distorted-tetrahedral geometry. Crystal structures of 1–3 contain 1-D supramolecular arrays constructed by intermolecular π⋯π interactions, with variations in π-stacking patterns. The ordered-layer-lattice or CH3CN is located between 1-D arrays. The absorption peaks of 1 and 2 in acetonitrile at room temperature display ILCT and MLCT absorptions. Emission experiments show solid-state emissions of 1 and 2 are not similar to those of solution samples. The conversion efficiency of 1 and 2 in dye-sensitized solar cells is extremely poor (<0.1%).

Ruthenium nitrosyl complexes [RuCl3(NO)(P–N)] bearing an oxazoline-derived P–N ligand (PHOX)

This work presents two complexes with general formula [RuCl3(NO)(PHOX)] (PHOX = 2-[2-(diphenylphosphino)phenyl]-4,4-dimethyl-2-oxazoline). Reaction of the PHOX ligand with [RuCl3(H2O)2(NO)] in refluxing methanol afforded fac-[RuCl3(NO)(PHOX)] (1), whereas exposure of a dichloromethane solution of complex 1 to ambient light gave mer,trans-[RuCl3(NO)(PHOX)] (2). On the other hand, reflux of complex 2 in methanol for 3 h resulted in thermal isomerization, to furnish complex 1. 1H and 31P NMR, elemental analysis, vibrational spectroscopy, UV–Vis, cyclic voltammetry, and X-ray diffractometry (for complex 2) aided characterization of the complexes. This work also compares the chemical properties of complexes 1 and 2 with the properties of similar complexes bearing PMA ([o-(N,N-dimethylamino)phenyl]diphenylphosphine, DPPE (1,2-bis(diphenylphosphino)ethane), and DPPP (1,3-bis(diphenylphosphino)propane); it also offers some insight into photo- and thermal isomerization mechanisms.

Pd(II) coordinated deprotonated diphenyl phosphino amino pyridine: reactivity towards solvent, base, and acid.

The reactivity and stability of P(III)-N and P(III)≈N bonds will be different towards various solvents, bases, and acids because of their difference in bond strength due to different N-pπ-P-dπ donor bonding. For this, a P≈N containing Pd(II) complex, [Pd(DPAP)2] (C1), was synthesized from the reaction between PdCl2(COD) (COD = 1,4-cyclooctadiene) and 2 equiv. DPAP (diphenyl phosphino amino pyridine) ligand, followed by deprotonation of the N-H proton of the coordinated DPAP. The reactivity and stability of coordinated P≈N in complex C1 were determined in various protic and aprotic solvents, bases, and acids. The inertness of coordinated P=N towards various solvents and bases was observed, whereas protonation occurs at the nitrogen of P=N in the presence of an acid to form P-NH, with the generation of dicationic palladium complexes (C2). The dicationic complex C2 is found to be stable in the presence of bulky monoanionic Sn(IV) reagents, whereas, in the presence of more nucleophilic anions like Br(-) or I(-), dissociation of one DPAP ligand from dicationic Pd(II) complexes C2 leads to the generation of Pd(DPAP)X2 (X = Br(-), I(-)). Finally, the utility of the complexes towards Suzuki coupling of various aryl bromides and aryl or heteraryl boronic acids has been checked.

Rate accelerations in the hydrogenation of furyl chalcones catalyzed by anchored montmorillonite diphenyl phosphino palladium(II) chloride

Rate accelerations in the hydrogenation of furyl chalcones catalyzed by anchored montmorillonite diphenyl phosphino palladium(II) chloride

Preparation of Iodide-Thiolate Bridged Binuclear Ni-Ni Complexes via Versatile Reaction of Labile Ni(II)-S(thiolate) Bond

The reaction between Fe(CO)4I2and Ni(SR)2(dppe) affords NiI2(dppe) due to the nucleophilic attack of iodide on the labile Ni-S(thiolate) bonds. The iodide-dithiolate-bridged binuclear Ni-Ni complexes [(dppe)Ni(µ-I)(µ-pdt)Ni(dppe)]I is readily prepared from the reaction between [NiI2(dppe)] and [Ni(pdt)(dppe)] [dppe = 1,2-bis(diphenyl phosphino)-ethane; pdt = 1,3-propane-dithiolate] in CH2Cl2as a result of attack on Ni-I bond by the lone pairs of electrons on thiolato sulfur donors. The reaction between [FeCp(CO)2I] and [Ni(pdt)(dppe)] in CH2Cl2processes extremely slowly. However, upon metathesis with NH4PF6, the iodide-thiolate bridged binuclear Ni-Ni complexes [(dppe)Ni(µ-I)(µ-pdt)Ni(dppe)]PF6is formed from the reaction of iodide and the Ni(II)-S bonds. The reaction between [NiCl2(dppe)] and NH4PF6and [Ni(pdt)(dppe)] gives a binuclear complex [(dppe)Ni(µ-pdt)Ni(dppe)]PF6without a halide-bridge. These results suggest that the reactivity of Ni-SR bonds in the Ni-thiolate-phosphine complexes is tunable with regard to the electronic environment of second metal ion and the different reactivity of iodide moiety. Electrochemical and crystallographic results are also analyzed for relevant compounds.

Synthesis, characterization and molecular structure of 1,1′ bis (diphenyl phosphino ferrocene) dioxide complex of the cis-uranyl dichloride

A 1,1′ bis(diphenyl phosphino ferrocene) dioxide complex of the uranyl dichloride was synthesized and characterized by elemental analysis, 1H, 31P{ 1H} NMR and X-ray diffraction methods. The structure of the compound shows that the uranium(VI) ion is surrounded by four oxygen and two chlorine atoms in an octahedral geometry. Two oxygen atoms from the bis (diphenyl phosphino ferrocene) dioxide and two chlorine atoms form a square planar arrangement. Two uranyl oxygen atoms occupy the axial positions. The bis(diphenyl phosphino ferrocene) dioxide ligand acts as a bidentate chelating ligand with a bite angle of 82.90(16)° around the uranyl group. The two chlorine atoms are mutually cis with a Cl–U–Cl angle of 97.75(7)°.

The double-helicate terpyridine silver(I) compound [Ag 2L 2](SO 3CF 3) 2 (L = 4′-phenyl-terpyridine) as a building block for di- and mononuclear complexes

The double-helicate dinuclear silver(I) complex [Ag 2L 2](SO 3CF 3) 2 ( 1) was obtained by reaction of AgSO 3CF 3 with 4′-phenyl-terpyridine (L). Each Ag + ion is coordinated by two N-atoms from one of the ligands and by one N-atom of the other ligand, forming an irregular Ag 2N 6 bi-triangle geometry, with a metallic bond between the two silver ions. Complex 1 reacts with potentially bidentate ligands (L 1), such as 9,10-bis(diphenylphosphino)anthracene (PAnP), 4,4′-dipyridyl or bis(diphenyl phosphino)methane (DPPM), to give the corresponding dinuclear complexes with bridging L 1, [Ag 2L 2(μ-L 1)](SO 3CF 3) 2 (L 1 = PAnP 2, 4,4′-dipyridyl 3 or DPPM 4), whereas on reaction with PPh 3 forms the mononuclear complex [AgL(PPh 3)](SO 3CF 3) 5. Reaction of 1 with the potentially tridentate ligand tris(2-diphenylphosphinoethyl)amine (NP 3) results in complete decomposition of the coordination spheres to form [Ag(NP 3)](SO 3CF 3) 6. Compound 1 shows a strong fluorescence in the solid state with its excitation band at 383.5 nm, the emission band at 535.5 nm and the lifetime of 4.20 ns, but the derived complexes do not show fluorescent properties. The photoluminescence of 1 in various solvents was also studied. The complexes were characterized by 1H NMR, elemental analysis, IR, MS, UV and single crystal X-ray diffraction.

Insertion of ethyl diazoacetate into the platinum–carbon bond of Pt(diphosphine)(halide)(aryl) complexes. X-ray structure of the Pt{(2S,4S)-bdpp)}I(Ph) complex

Pt(diphosphine)X(aryl) complexes [diphosphine = 1,3-bis(diphenylphosphino)propane (dppp), 2,4-bis(diphenylphos phino)pentane (bdpp); aryl = phenyl, 2-thiophenyl; X = Cl, I] have been reacted with ethyl diazoacetate in chloroform. It has been revealed by in␣situ n.m.r. studies that the starting compounds insert the carbene, formed from ethyl diazoacetate, into the Pt–aryl group resulting in Pt(diphosphine)X{CH(aryl)COOC2H5}. Depending on the reaction conditions (reaction time, ratio of the reactants) and the ligands various side-reactions have been observed: (i) the formation of Pt(diphosphine)X2 in chloroform, (ii) the insertion of the :CHCOOC2H5 fragment into the Pt–halide bond of the dihalogeno complexes Pt(diphosphine)X2 resulting in the exclusive formation of Pt(diphosphine)X(CHXCOOC2H5). Diastereoselective insertion reactions have been observed in the presence of (S,S)-bdpp as diphosphine. The Pt{(S,S)-bdpp)}I(Ph) complex has been characterized by X-ray crystallography.

Preparation and electronic properties of rhenium(V) complexes with bis(diphenyl phosphino)ethane

Complexes of bis(diphenylphosphino)ethane (dppe) of the types ReOX3(dppe) and ReO(OR)X2(dppe) (with X= Cl or Br, and R = Me, Et, Pr, Ph, cyclohexyl (Cy), or -CH2CH2OH) were prepared to evaluate the influence of ligand changes on the low-energy d–d transitions in these Re(V) low-spin d2 systems. Arylimido compounds Re(NR)Cl3(dppe) (with R = Ph and p-ClC6H4) were also obtained. X-ray diffraction studies on ReO(OPr)Cl2(dppe), ReO(OPh)Br2(dppe), and ReO(OCy)Cl2(dppe) confirmed the presence of the trans O=Re-OR unit and showed that the structural characteristics of the Re-O-R segment are not affected by the presence of a bulky cyclohexyl substituent or an aromatic phenyl group. The structure of the arylimido complex Re(p-ClC6H4N)Cl3(dppe) was also determined. The electronic absorption spectra of the ReOX3(dppe) compounds include two low-energy components at ~11 500 and ~16 000 cm–1, assigned to the two spin-allowed d–d transitions expected for these low-symmetry systems. Substitution of the oxo ligand by an arylimido group has little effect on the lower-energy component, but moves the two components closer together. Replacing the halogen trans to the Re=O bond by an alkoxo group shifts the whole system to higher energies. These variations were found to correlate well with the energies of the frontier orbitals determined from DFT calculations. While attempting to prepare ReOCl3(dppe) from ReOCl3(PPh3)2, the Re(III) compound fac-ReCl3(PPh3){Ph2PC2H4PPh2(O)} was obtained, in which one end of dppe had become a phosphine oxide. Upon standing in DMSO, this compound gave the octahedral compound ReCl4{Ph2PC2H4PPh2(O)}, in which the formation of a chelate ring involving a phosphine and a phosphine oxide was ascertained by X-ray diffraction.Key words: rhenium, crystal structure, DFT calculations, d–d electron transitions.

The synthesis and structural characterization of linear and macrocyclic bis(dinitrosyliron) complexes supported by bis(phosphine) bridging ligands

Reactions involving Fe(NO)2(CO)2 and the bis(phosphine) ligands bis(diphenylphosphino)methane (DPPM), bis(diphenylphosphino)acetylene (DPPA), 1,6-bis(diphenylphosphino)hexane (DPPH), and 1,4-bis(diphenyl phosphino)benzene (DPPB) have been examined. From these reactions, the mononuclear complex, Fe(κ1-DPPM)(NO)2(CO) 3, linear dinuclear species of the type Fe2(µ-L)(NO)4(CO)2 (L = Ph2PCH2PPh2 4, Ph2PC[Formula: see text]CPPh2 5, Ph2PCH2(CH3)4CH2PPh2 6, and Ph2P(p-C6H4)PPh2 7), and macrocyclic dinuclear species of the type Fe2(µ-L)2(NO)4 (L = Ph2PCH2PPh2 8 and Ph2PC[Formula: see text]CPPh2 9) were isolated and spectroscopically characterized. For 4, 5, 8, and 9, the solid-state molecular structures of the products were determined by use of single-crystal X-ray diffraction techniques. Key words: dinitrosyliron, iron nitrosyls, dinuclear macrocycles, bis(phosphine) complexes.

Phosphate and Phosphate Analogue Complexes of Uranyl Nitrate

In the Purex process the selective uranium and plutonium extraction (and back extraction) from nitric acid into 30% tri butyl phosphate/ odourless kerosene is used to separate uranium and plutonium from each other and fission products in spent nuclear fuel recycle process. The presence of dibutyl phosphate (a tributyl phosphate degradation product) can inhibit the uranium (and plutonium) back extraction process by forming very stable solvent phase complexes with these actinides. However, the types of complexes that exist and prevent back extraction have not been fully characterised. A model compound approach has been adopted in which the co-ordination chemistry of UO22+ with a range of P=0 and P(0)OH ligands have been studied. These complexes have been characterised using spectroscopic techniques including IR, Raman, UV7 vis, 31NMR NMR, and by single crystal X-ray diffraction to assess their utility in identifying molecular species under extraction conditions. We report full structural characterisation of [UO2(NO3)2(MDPhP)2], [UO2(NO3)DppmO2] and [UO2(Dpp)2(MeOH)] where MDPhP = methyl diphenyl phosphine oxide, Dpp = diphenyl phosphate and DppmO2 = Bis(diphenyl phosphino) methane dioxide

The influence of metal coordination on ligand geometry: the structure of 2-(diphenylphosphino)acetophenone and bis(2-(diphenylphosphino)acetophenone)palladium(II)bistriflate

The structures of 2(diphenylphosphino)acetophenone and bis(2(diphenyl phosphino)acetophenone)palladium(II)bistriflate have been determined by X-ray crystallography. The ligand is of interest because its P,O donor set combines the hard and soft properties. In the Pd-complex, which was prepared by treating tetrakisacetonitrile-palladium-bistriflate with 2-(diphenylphosphino)acetophenone in dichloromethane for 4h at room temperature, the O-coordination provides a masked coordinative unsaturation.The ligand crystallises in the monoclinic space group P21/c with cell dimensions a=11.050(2), b=16.052(3), c=9.7082(19)Å,β=109.58(3)°, V=1622.4(6)Å3 and Z=4, synchrotron radiation, λ=0.8520Å. The Pd-complex crystallises in the orthorhombic space group P212121 with cell dimensions a=11.867(2), b=18.162(4), c=19.603(4)Å,V=4224.9(15)Å3 and Z=4, MoKα radiation. Both structures were solved by direct methods and the refinements resulted in the R-values of 0.059 and 0.043, for the organic compound and the palladium compound, respectively.Two bi-dentate ligand binds to palladium(II) in a cis-configuration. The Pd–O distances are 2.060(3) and 2.096(2)Å and the Pd–P distances 2.2290(10) and 2.2294(10)Å, showing a large trans-influence of the phosphorus atoms. Half-normal probability plot analyses indicate that the s.u.'s are largely underestimated in the investigated structures. The bond-angles around the phosphorus atom and the orientation of the keto-substituted phenyl rings as well as the orientation of the keto-groups are highly affected by metal complexation.