X-ray photoelectron spectroscopy of alkaline earth metal uranate complexes

Summary X-ray photoelectron spectra for MgUO_4–x, MgU₃O_8.9, CaUO_4–x, Ca₂UO₅, Ca₃UO₆, Ca₂U₃O₁₁, CaU₂O₇, CaU₄O₁₂, SrUO₄, SrUO_3.67, Sr₂U₃O₁₁, SrU₄O_12.8, Sr₂UO₅, Sr₃UO₆, BaUO₄, Ba₃UO₆, BaU₂O₇, Ba₂U₂O₇ and Ba₂U₃O₁₁ have been recorded.Recorded O(1s) peak positions range from 529.5 to 533.4 eV and certain trends can be related to data obtained from other studies. By contrast, the range of U(4f) peak positions is much smaller totalling 0.7 eV. All compounds show satellite structure to the high binding energy side of the U(4f) peaks. Satellites separated byca. 10 eV from the main peaks are assigned to a transition from the uranium-oxygen bonding band to the U(6d) conduction band.     

X-ray photoelectron spectra of polynuclear manganese complexes

Manganese trimethylacetate complexes with different ligand environments were studied by X-ray photoelectron spectroscopy (XPS). Changes in the Mn 2p, C 1s, O 1s, and N 1s X-ray photoelectron spectra caused by the substitution of Mn → N coordination bonds for Mn → O coordination bonds were examined. In the spectra of manganese trimethylacetate complexes, the satellite component was identified, which is evidence of the high-spin state of manganese atoms. An increase in the magnetic moment of the manganese complexes, both with the oxygen and mixed oxygen-nitrogen environment, is accompanied by an increase in the spin-orbit splitting, the difference in E _b between the satellite and the Mn 2p _3/2 line, and the ratio between the integrated intensities of the satellite and the Mn 2p _3/2 line (I sat_3/2/I Mn 2p _3/2). The XPS data made it possible to determine the measure of covalence of the metal-ligand bond. The XPS results are consistent with X-ray crystallography data.     

X-ray photoelectron spectra of polyhydrido complexes of tungsten and molybdenum

X-Ray photoelectron spectroscopy has been applied to study MH₄L₄(M = or Mo, L = PHPh₂, PMePh₂, PEtPh₂, PBuPh₂, PEt₂Ph, P(OPr-i)₃ or $\text{1}\text{2}$ dppe). It has been shown that tungsten in these compounds has a negative charge whereas the charge of molybdenum is almost zero.     

X-ray photoelectron spectra of metal complexes of substituted 2,4-pentanediones

The X-ray photoelectron spectra of 14 complexes of Al³⁺, Cr ³⁺, Fe³⁺, Co³⁺ and Cu²⁺ with 3-X-2,4-pentanedione (X = H, Cl, Br) were determined to analyse the nature of metal-ligand bonding in these complexes. The trend in the position of np photoelectron lines of X-group with a change of metal ion was decided by the relative contribution of metal-toligand and ligand-to-metal charge transfer. The analysis of the satellites in the M(2p_3/2) and M(2p_1/2) spectra suggested that the metal-ligand bond in the chromium(III) complex had higher covalent character than that in the iron(III) complex. The satellite separations in the O(1s) spectra of M(3-Xptdn)₃ were in the range 4.0-4.8 eV: these satellites were assigned to a shake-up transition of Lπ → Lπ^* character. The O(1s) spectra of Fe(3-Xptdn)₃ and A1(3-Xptdn)₃ displayed an additional strong peak to higher energy than that of the main peak (δE = 2.1–3.1 eV) when the samples of complexes were bombarded with argon ions for a longer time.     

Reaction of small molecules O2, NO,CO, and the Naldini salt (PPh3)2MnBr2: Characterized by infrared spectroscopy,elemental analysis,and single-crystal X-ray diffraction

Addition of 2 equiv. of PPh₃ to MnBr₂ in tetrahydrofuran (THF) solution under N₂ atmosphere results in the formation of Naldini salt (PPh₃)₂MnBr₂ ( 1 ). Reaction of Complex 1 and O₂, NO, and CO (with reducing agent) leads to Complex (OPPh₃)₂MnBr₂ ( 2 ), (PPh₃)₂Mn(NO)Br₂ ( 3 ), and (PPh₃)₂Mn(CO)₃Br ( 4 ), respectively. Both Complexes 2 and 4 crystallize in the triclinic space group P-1 with a = 9.94 Å, b = 10.11 Å, c = 10.53 Å; α = 65.42°, β = 63.16°, and γ = 89.22° of 2 and a = 10.23 Å, b = 12.26 Å, c = 14.44 Å and α = 97.03°, β = 104.34°, and γ = 106.33° of 4 . The isoelectronic replacement of 3CO with 2NO yields the {Mn(NO)₂}⁸ species (PPh₃)₂Mn(NO)₂Br ( 5 ). The single crystal of 5 is in the monoclinic space group C2/c with a = 23.17 Å, b = 9.62 Å, c = 15.92 Å, and β = 114.91°. In the THF solution, Complex 5 serves as an NO source in the presence of NO trapping, Co(TPP), Co(TPP) = 5,10,15,20-tetraphenyl-21H,23H-porphine cobalt(II).     

Oxidation – Reduction Reactions of Tetrachloroaurate(III) Anion with Triphenyl Derivatives of Group V Elements

The reduction of the tetrachloroaurate (III) anion by L (L = PPh₃, AsPh₃, SbPh₃) is quantitative in non-aqueous solution. The products are the gold(I)-complexes AuClL (L = AsPh₃, SbPh₃) and Au(PPh₃)⁺₂ together with the corresponding oxidation product LCl₂. Kinetic studies show that the reactions are first order in AuCl^?₁ and L. In addition a path independent of PPh₃ was found in dichloromethane. These data are interpreted in terms of mechanisms which involve reduction of AuCl^?₄ to AuCl^?₂ followed by equilibrium formation of AuClL for L = AsPh₃ and SbPh₃. For PPh₃, the data are consistent with a chloride replacement by PPh₃ to give AuCl₃ PPh₃, which is followed by a rapid reduction by a second mole of PPh₃. Equilibrium formation constants are reported for several Au(I) complexes.     

Halonickel(I) complexes

Summary The reduction of nickel(II) halides with NaBH₄ in the presence of different ligands, L=PPh₃, AsPh₃, SbPh₃, has been studied. With a molar ratio L/Ni=3, new complexes NiX(SbPh₃)₃, X=Cl, Br, I, were obtained. With a molar ratio L/Ni=2, dimeric species [NiXL₂]₂, X=Cl, Br, I; L=PPh₃, AsPh₃, SbPh₃, were isolated. They are unstable and decompose easily in the solid and rapidly in solution, so that pure samples were only identified for X=Cl, L=PPh₃, AsPh₃, SbPh₃; X=Br, L=PPh₃ and X=I, L=PPh₃. With a molar ratio L/Ni=1, complexes [NiXL]_n (probably polymeric) were obtained. They are very unstable and pure samples could only be isolated when X=Cl, L=PPh₃. Impure substances containing variable amounts of decomposition products were obtained in all the remaining cases. The chemical and structural behaviour of these complexes is discussed.     

Erratum

The hydrido-thiocarbonyl osmium(II) complexes OsH₂(CS)(PPh₃)₃, OsHCl(CS)(PPh₃)₃, OsH(OClO₃)(CS)(PPh₃)₃, OsHCl(CS)(CNR)(PPh₃)₂ and [OsH(CS)(CO)(PPh₃)₃]⁺, (R = p-tolyl), have been derived from OsCl₂(CS)(PPh₃)₃ and [OsH(CS)(CO)(PPh₃)₃]⁺, the latter can be deprotonated to give the zerolavent complex, Os(CS)(CO)(PPh₃)₃.     

Pseudohalogenometallverbindungen: LVIII. Reaktionen von diphenylphosphorylazid und perfluor-n-hexylsulfonylazid mit triphenylphosphan-komplexen von platin(0), rhodium(I), iridium(I), ruthenium(0), kobalt(II) und kupfer(I)

Diphenylphosphorylazide N₃P(O)(OPh)₂ reacts with Pt(PPh₃)₃, Pt(PPh₃)₂(C₂H₄), trans-RhCl(CO)(PPh₃)₂, Ru(CO)₃(PPh₃)₂, CoCl₂(PPh₃)₂ and CuCl(PPh₃)₂ to give the azido complexes Pt(PPh₃)₂(N₃)R, Pt(PPh₃)₂(N₃)₂R₂, the urylene complex RhCl(PPh₃)₂(RNCONR) and the phosphine imine complexes Ru(CO)₃(RPPh₃)₂, CoCl₂(RNPPh₃)₂, CuCl(RNPPh₃)₂, respectively, (RP(O)(OPh)₂). The oxidative addition of n-C₆F₁₃SO₂N₃ to Pt(PPh₃)₄ and Pt(PPh₃)₂(C₂H₄) affords the complexes Pt(PPh₃)₂(N₃)R and Pt(PPh₃)₂(N₃)₂R₂, respectively, (RSO₂C₆F₁₃. The compounds are characterized by elemental analysis and by their IR spectra.     

X-ray photoelectron spectra and structure of polynuclear nickel complexes

Mono- and binuclear nickel complexes of different stoichiometry have been studied by X-ray photoelectron spectroscopy (XPS). The Ni2p, Ni3p, and N1s X-ray photoelectron spectra have been examined, and the role of a ligand in their formation has been determined. As distinct from a low-spin Ni(II) complex, the Ni2p spectra of high-spin Ni(II) compounds show strong satellite lines. For high-spin Ni(II) complexes, which have unpaired 3d electrons, the Ni2p _1/2-Ni2p _3/2 spin-orbit splitting is larger than that for a low-spin Ni(II) compound. The presence or absence of the satellite structure has made it possible to classify these complexes with regard to their magnetic properties. The difference between the Ni2p _3/2 and N1s binding energies has made it possible to estimate the covalence of the metal-ligand bond. The XPS results are consistent with X-ray crystallography data.     

The tris(triphenylphosphine)osmium zerovalent complexes Os(CO)2(PPh3)3, .Os(CO)(CNR)(PPh3)3, Os(CO)(CS)(PPh3)3, Os(CS)(cNR)(PPh3)3 and derived compounds

Detailed procedures for the syntheses of Os(CO)₂(PPh₃)₃, Os(CO)(CNR)-(PPh₃)₃ (R = p-tolyl), Os(CO)(CS)(PPh₃)₃ and Os(CS)(CNR)(PPh₃)₃, together with the derived complexes Os(CO)₂(CS)(PPh₃)₂, Os(CO)(CS)(CNR)(PPh₃)₂, Os(η²-C₂H₄)(CO)(CNR)(PPh₃)₂, Os(η²-C₂H₄)(CO)(CS)(PPh₃)₂, Os(η²CS₂)(CO)₂-(PPh₃)₂, Os(η²CS₂)(CO)(CS)(PPh₃)₂, Os(η²-CS₂)(CO)(CNR)(PPh₃)₂, Os(η²PhC₂Ph)(CO)₂(PPh₃)₂ and OsH(C2Ph)(CO)₂(PPh₃)₂ are described.     

X-ray photoelectron spectra and structure of cobalt compounds with N-heterocyclic ligands

The electronic structure of cobalt complexes with bi-, tri-, and tetradentate ligands and the mutual influence of ligands in them have been studied by X-ray photoelectron spectroscopy. The Co2p, N1s, and O1s photoelectron spectra have been studied. Unlike low-spin Co(III) complexes, the high-spin Co(II) compound exhibits a strong satellite line in the Co2p spectrum. For the high-spin Co(II) compound having unpaired 3d electrons, the Co2p _1/2-Co2p _3/2 spin-orbit splitting is larger than that in the low-spin Co(III) complexes. All cobalt complexes under consideration contain strongly bound dioxygen, which can be considered an inherent structural unit.     

Convenient laboratory synthesis of vinylic silicon compounds via the reactions of acetylene with hydrosilanes catalyzed by group-VIII metal phosphine complexes

The hydrosilylation of acetylene (HCCH) with trichlorosilane, triethoxysilane, methyldichlorosilane, methyldiethoxysilane and $\text{n}$-hexyldichlorosilane in an inert solvent in the presence of various phosphine complexes of Group-VIII metals such as Ru, Rh, Pd and Pt, as well as chloroplatinic acid, was investigated. Among the complexes studied, RuCL₂ (PPh₃)₃, PtCl₂ (PPh₃)₂, RhCl (PPh₃)₃, RhH(PPh₃)₄ and Pt(PPh₃)₄ were found to be the catalysts of choice for the selective syntheses of vinyltrichlorosilane, vinyltriethoxysilane, methylvinyldichlorosilane, methylvinyldiethoxysilane and $\text{n}$-hexylvinyldichlorosilane, respectively.     

Cluster chemistry: XXIII. Mono-, di- and tri-auration of H4Ru4(CO)12 with [{Au(PPh3)}3O][BF4]: X-ray crystal structure of HRu4Au3(CO)12(PPh3)3

Reactions between [H₃Ru₄(CO)₁₂]^? and [{Au(PPh₃)}₃O]⁺ afford H₃Ru₄-Au(CO)₁₂(PPh₃), H₂Ru₄Au₂(CO)₁₂(PPh₃)₂ and HRu₄Au₃(CO)₁₂(PPh₃)₃. The X-ray structure of the latter shows that it has the unusual bicapped trigonal bipyramidal metal core, in which two Ru₂Au faces of the Ru₄Au fragment are capped by the other two Au atoms. The central Au atom is asymmetrically attached to the Ru₃ face as a result of the interaction of a phenyl ring of the PPh₃ ligand with two of the CO groups. Metal-metal separations are: two Au-Au, 2.837(1) Å; Ru-Ru, six between 2.805–3.004(3) Å; Au-Ru, seven between 2.821–3.007(2) Å. HRu₄Au₃(CO)₁₂(PPh₃)₃ is monoclinic, space group P2₁/n, with a 18.754(3), b 18.459(5), c 22.317(4) Å, β 113.06(2)°; 2852 data [I > 2.5σ(I)] were refined to R, R_w 0.038, 0.038.     

The synthesis and structure of bis-μ-(diphenylphosphido)dicarbonylbis(triphenylphosphine)diiridium

The reaction of IrH(CO)(PPh₃)₃ in boiling decalin gives a purple crystalline product which X-ray diffraction establishes as [Ir(PPh₂)(CO)(PPh₃)]₂, a complex containing a metalmetal bond of length 2.554Å and order two.     

Isocyanid- und heteroallen-verbrückte metallkomplexe : V. μ3-CS2-komplexe

Purple IrCl₃(CCl₂)(PPh₃)₂ results from reaction between IrHCl₂(PPh₃)₃ and Hg(CCl₃)₂. X-ray crystal structure determination reveals an octahedral complex with trans-phosphine ligands and a short IrC distance to the CCl₂ ligand of 1.872(7) Å, compatible with an iridiumcarbon double bond. Chloride is easily displaced from the dichlorocarbene ligand and the products which have been derived include IrCl₃(CO)(PPh₃)₂, IrCl₃(CS)(PPh₃)₂, IrCl₃(CNMe)(PPh₃)₂, IrCl₃(CClNMe₂)(PPh₃)₂, IrCl₃(CNHCH₂CH₂NH)(PPh₃)₂ and IrCl(CSCH₂CH₂S)-(PPh₃)₂.     

Synthesis of ylideplatinum(II) complexes via α-functionalised alkylplatinum(II) intermediates and some comparative data on palladium(II) complexes; X-ray structure of trans-[Pt(CH2PEt3)I(PEt3)2]I

The reaction of [Pt(PEt₃)₃] with CH₂I₂ affords trans-[Pt(CH₂PEt₃)I(PEt₃)₂]I and is believed to proceed via the α-functionalised alkyl cis-[Pt(CH₂I)I(PEt₃)₂], because similar ylides are obtained from cis- or trans-[PT(CH₂X)(PPh₃)₂X] (XCl, Br, or I) with PR₃ (PEt₃, PBu₃ⁿ, PMePh₂, PEtPh₂, or PPh₃); cis-[Pd(CH₂I)-I(PPh₃)₂] does not react with excess PPh₃, but with PEt₃ yields trans-[Pd(CH₂PEt₃)I(PPh₃)₂]I; the X-ray structure of trans-[Pt(CH₂PEt₃)I(PEt₃)₂]I (current R = 0.045) shows PtP(1) 2.332(7), PtP(2) 2.341(8), PtC 2.08(2), and PtI 2.666(2) Å, and angles (a) C(1)PtI, P(1), P(2): 176.9(8), 91.6(6), 93.4(6), (b) IPtP(1), P(2): 87.1(2), 88.5(2), and (c) P(1)P(2), 166.8(3), and (d) PtC(1)P(3), 118(1)°.     

X-ray photoelectron study of the electronic structure of Fe systems

The possibility of magnetic property investigations and obtaining additional information is examined for compounds with various types of chemical bond, namely, FeX₂ (X = F, Cl, Br), Fe-Ge, Fe₅₀Co₅₀, and Fe₅₀Mn₅₀, using X-ray photoelectron spectroscopy. Translated fromZhurnal Struktumoi Khimii, Vol. 39, No. 6, pp. 1093–1097, November–December, 1998.     

Synthesis, X-ray studies, spectroscopic characterization and DFT calculations of p-tolylimido rhenium(V) complexes bearing an imidazole-based ligand

Novel p-tolylimido rhenium(V) complexes [Re(p-NC₆H₄CH₃)X₂(hpb)(PPh₃)] and [Re(p-NC₆H₄CH₃)(hpb)₂(PPh₃)]X (X = Cl, Br) have been obtained in the reactions of [Re(p-NC₆H₄CH₃)X₃(PPh₃)₂] with 2-(2-hydroxyphenyl)-1H-benzimidazole (Hhpb). The compounds were identified by elemental analysis IR, UV-Vis spectroscopy and X-ray crystallography. The electronic structures of the complex [Re(p-NC₆H₄CH₃)Cl₂(hpb)(PPh₃)] and the cation [Re(p-NC₆H₄CH₃)(hpb)₂(PPh₃)]⁺ have been calculated with the density functional theory (DFT) method. Additional information about binding in the [Re(p-NC₆H₄CH₃)Cl₂(hpb)(PPh₃)] and [Re(p-NC₆H₄CH₃)(hpb)₂(PPh₃)]⁺ has been obtained by NBO analysis. The electronic spectra of [Re(p-NC₆H₄CH₃)Cl₂(hpb)(PPh₃)] and [Re(p-NC₆H₄CH₃)(hpb)₂(PPh₃)]Cl were investigated at the TDDFT level employing B3LYP functional in combination with LANL2DZ.     

Cyclopentadienyl ruthenium and osmium complexes : II. The reactivity of π-cyclopentadienyl(triphenylphosphine)-ruthenium(II) and -osmium(II) complexes

Ruthenium and osmium complexes of the type CpMX(PPh₃)L (M = Ru; X = Cl, H, S₂COC₁₀H₁₉, S₂COMe; L & PPh₃ and PHPh₂; M = Os, X = Cl, Br, I, H, D, xanthogenate, dithiocarbamate, BPh₄, L = PPh₃). The compound CpOsCl(PPh₃)₂ is readily soluble in MeOH and in the solution the cation [CpOs(PPh₃)₂]⁺ is present. Upon addition of NaBPh₄ a white compound CpOs(PPh₃)₂BPh₄ immediately precipitates, which can not be solved in MeOH, contrary to the behaviour of the corresponding ruthenium compound.