Neue phosphidoverbrückte Mehrkernkomplexe des Ag und Zn. Die Kristallstrukturen von [Ag3(PPh2)3(PnBu2tBu)3], [Ag4(PPh2)4(PR3)4] (PR3 = PMenPr2, PnPr3), [Ag4(PPh2)4(PEt3)4]n, [Zn4(PPh2)4Cl4(PRR2)2] (PRR′2 = PMenPr2, PnBu3, PEt2Ph), [Zn4(PhPSiMe3)4Cl4(C4H8O)2] und [Zn4(PtBu2)4Cl4]

New Phosphido-bridged Multinuclear Complexes of Ag and Zn. The Crystal Structures of [Ag₃(PPh₂)₃(PⁿBu₂^tBu)₃], [Ag₄(PPh₂)₄(PR₃)₄] (PR₃ = PMeⁿPr₂, PⁿPr₃), [Ag₄(PPh₂)₄(PEt₃)₄]_n, [Zn₄(PPh₂)₄Cl₄(PRR′₂)₂] (PRR′₂ = PMeⁿPr₂, PⁿBu₃, PEt₂Ph), [Zn₄(PhPSiMe₃)₄Cl₄(C₄H₈O)₂] and [Zn₄(P^tBu₂)₄Cl₄] AgCl reacts with Ph₂PSiMe₃ in the presence of tertiary Phosphines (PⁿBu₂^tBu, PMeⁿPr₂, PⁿPr₃ and PEt₃) to form the multinuclear complexes [Ag₃(PPh₂)₃(PⁿBu₂^tBu)₃] 1 , [Ag₄(PPh₂)₄(PR₃)₄] (PR₃ = PMeⁿPr₂ 2 , PⁿPr₃ 3 ) and [Ag₄(PPh₂)₄(PEt₃)₄]_n 4 . In analogy to that ZnCl₂ reacts with Ph₂PSiMe₃ and PRR′₂ to form the multinuclear complexes [Zn₄(PPh₂)₄Cl₄(PRR′₂)₂] (PRR′₂ = PMeⁿPr₂ 5 , PⁿBu₃ 6 , PEt₂Ph 7 ). Further it was possible to obtain the compounds [Zn₄(PhPSiMe₃)₄Cl₄(C₄H₈O)₂] 8 and [Zn₄(P^tBu₂)₄Cl₄] 9 by reaction of ZnCl₂ with PhP(SiMe₃)₂ and ^tBu₂PSiMe₃, respectively. The structures were characterized by X-ray single crystal structure analysis. Crystallographic data see “Inhaltsübersicht”.     

Synthesis and Characterization of Two Uranyl-Aryl “Ate” Complexes

Reaction of [UO₂Cl₂(THF)₃] with 3 equivalents of LiC₆Cl₅ in Et₂O resulted in the formation of first uranyl aryl complex [Li(Et₂O)₂(THF)][UO₂(C₆Cl₅)₃] ([Li][ 1 ]) in good yields. Subsequent dissolution of [Li][ 1 ] in THF resulted in conversion into [Li(THF)₄][UO₂(C₆Cl₅)₃(THF)] ([Li][ 2 ]), also in good yields. DFT calculations reveal that the U−C bonds in [Li][ 1 ] and [Li][ 2 ] exhibit appreciable covalency. Additionally, the ¹³C NMR chemical shifts for their C_ipso environments are strongly affected by spin-orbit coupling—a consequence of 5f orbital participation in the U−C bonds.     

Mononitrosyl‐ und trans‐Dinitrosyl‐Komplexe von Phthalocyaninaten des Mangans und Rheniums

Mononitrosyl and trans ‐Dinitrosyl Complexes of Phthalocyaninates of Manganese and Rhenium Tetra(n‐butyl)ammonium or di(triphenylphosphane)iminium nitrosylacidophthalocyaninato(2–)manganate, (cat)[Mn(NO)(X)pc^2–] (X = ONO, NCO, N₃; cat = ⁿBu₄N, PNP) is prepared from acidophthalocyaninato(2–)manganese, [Mn(X)pc^2–], (cat)NO₂ and (ⁿBu₄N)BH₄ in CH₂Cl₂ or from nitrosylphthalocyaninato(2–)manganese, [Mn(NO)pc^2–] and (ⁿBu₄N)X (X = ONO, NCO, N₃, NCS) at T < 120 °C, respectively. [Mn(NO)(X)pc^2–]^– dissociates in methanol, and [Mn(NO)pc^2–] precipitates. Nitrito(O)phthalocyaninato(2–)manganese, (cat)NO₂ and hydrogensulfide yield trans‐di(nitrosyl)phthalocyaninato(2–)manganate, ^trans[Mn(NO)₂pc^2–]^–, isolated as red violet (PNP) and (ⁿBu₄N) complex salt. Nitrosyl(triphenylphosphane oxide)phthalocyaninato(2–)manganese, [Mn(NO)(OPPh₃)pc^2–] is obtained by addition of OPPh₃ to [Mn(NO)pc^2–] at 200 °C. Di(triphenylphosphane)phthalocyaninato(2–)rhenium(II) and (PNP)NO₂ in CH₂Cl₂ or in molten (PNP)NO₂ and PPh₃ at 100 °C yields green blue l‐di(triphenylphosphane)iminium nitrosylnitrito(O)phthalocyaninato(2–)rhenate, ^l(PNP)[Re(NO)(ONO)pc^2–]. Similarly, but with (ⁿBu₄N)NO₂ red plates of tetra‐(n‐butyl)ammonium trans‐di(nitrosyl)phthalocyaninato(2–)rhenate, (ⁿBu₄N)^trans[Re(NO)₂pc^2–] is isolated. Addition of (PNP)Br or (PNP)PF₆ to a concentrated solution of (ⁿBu₄N)^trans[Re(NO)₂pc^2–] in pyridine precipitates ^l(PNP)^trans[Re(NO)₂pc^2–]. (ⁿBu₄N)^trans[Re(NO)₂pc^2–] and PPh₃ at 300 °C yield blue green nitrosyl(triphenylphosphane oxide)phthalocyaninato(2–)‐ rhenium, [Re(NO)(OPPh₃)pc^2–], that is oxidised with iodine precipitating nitrosyl(triphenylphosphane oxide)phthalocyaninato(2–)rhenium triiodide, [Re(NO)(OPPh₃)pc^2–]I₃. The crystal structures of ^l(PNP)[Mn(NO)(ONO)pc^2–] ( 1 ), ^l(PNP)‐ [Mn(NO)(NCO)pc^2–] ( 2 ), ^l(PNP)^trans[Mn(NO)₂pc^2–] ( 3 ), ^l(PNP)^trans[Re(NO)₂pc^2–] ( 4 ) [Mn(NO)(OPPh₃)pc^2–] ( 5 ), [Re(NO)(OPPh₃)pc^2–] ( 6 ), and [Re(NO)(OPPh₃)pc^2–]I₃ · CH₂Cl₂ ( 7 ) have been determined. The M–N(NO) distance varies between 1.623(12) Å in 5 and 1.846(3) Å in 3 . The M–N–O moiety is almost linear. The UV‐Vis spectra with the B band at ca. 14500 cm^–1and the Q band at 30400 cm^–1 do not dependent significantly on the axial ligand and the metal atom and its oxidation state. N–O stretching vibrations are observed in the IR spectra between 1701 cm^–1 in 3 and 1753 cm^–1 in [Mn(NO)pc^2–] or for the Re series between 1571 cm^–1 in 4 and 1724 cm^–1 in 7 . M–N(NO) stretching and M–N–O deformation vibrations are assigned in the IR spectra and resonance Raman spectra between 486 cm^–1 in 4 and 620 cm^–1 in 1 .     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [Pt(N3)6]2– und [Pt(N3)Cl5]2–, 195Pt‐ und 15N‐NMR‐Spektren von [Pt(N3)nCl6–n]2– und [Pt(15NN2)n(N215N)6–n]2–, n = 0–6

Synthesis, Crystal Structures, and Vibrational Spectra of [Pt(N₃)₆]^2– and [Pt(N₃)Cl₅]^2–, ¹⁹⁵Pt and ¹⁵N NMR Spectra of [Pt(N₃)_nCl_6–n]^2– and [Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n]^2–, n = 0–6 By ligand exchange of [PtCl₆]^2– with sodium azide mixed complexes of the series [Pt(N₃)_nCl_6–n]^2– and with ¹⁵N‐labelled sodium azide (Na¹⁵NN₂) mixtures of the isotopomeres [Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n]^2–, n = 0–6 and the pair [Pt(¹⁵NN₂)Cl₅]^2–/[Pt(N₂¹⁵N)Cl₅]^2– are formed. X‐ray structure determinations on single crystals of (Ph₄P)₂[Pt(N₃)₆] ( 1 ) (triclinic, space group P1, a = 10.175(1), b = 10.516(1), c = 12.380(2) Å, α = 87.822(9), β = 73.822(9), γ = 67.987(8)°, Z = 1) and (Ph₄As)₂[Pt(N₃)Cl₅] · HCON(CH₃)₂ ( 2 ) (triclinic, space group P1, a = 10.068(2), b = 11.001(2), c = 23.658(5) Å, α = 101.196(14), β = 93.977(15), γ = 101.484(13)°, Z = 2) have been performed. The bond lengths are Pt–N = 2.088 ( 1 ), 2.105 ( 2 ) and Pt–Cl = 2.318 Å ( 2 ). The approximate linear azido ligands with N^α–N^β–N^γ‐angles = 173.5–174.6° are bonded with Pt–N^α–N^β‐angles = 116.4–121.0°. In the vibrational spectra the PtCl stretching vibrations of (n‐Bu₄N)₂[Pt(N₃)Cl₅] are observed at 318–345, the PtN stretching modes of (n‐Bu₄N)₂[Pt(N₃)₆] at 401–428 and of (n‐Bu₄N)₂[Pt(N₃)Cl₅] at 408–413 cm^–1. The mixtures (n‐Bu₄N)₂[Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n], n = 0–6 and (n‐Bu₄N)₂[Pt(¹⁵NN₂)Cl₅]/(n‐Bu₄N)₂[Pt(N₂¹⁵N)Cl₅] exhibit ¹⁵N‐isotopic shifts up to 20 cm^–1. Based on the molecular parameters of the X‐ray determinations the vibrational spectra are assigned by normal coordinate analysis. The average valence force constants are f_d(PtCl) = 1.93, f_d(PtN^α) = 2.38 and f_d(N^αN^β, N^βN^γ) = 12.39 mdyn/Å. In the ¹⁹⁵Pt NMR spectrum of [Pt(N₃)_nCl_6–n]^2–, n = 0–6 downfield shifts with the increasing number of azido ligands are observed in the range 4766–5067 ppm. The ¹⁵N NMR spectrum of (n‐Bu₄N)₂[Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n], n = 0–6 exhibits by ¹⁵N–¹⁹⁵Pt coupling a pseudotriplett at –307.5 ppm. Due to the isotopomeres n = 0–5 for terminal ¹⁵N six well‐resolved signals with distances of 0.03 ppm are observed in the low field region at –201 to –199 ppm.     

Thiosemicarbazone Complexes of Uranium

Acetylpyridine thiosemicarbazone, HAPTSC ( 1 ), reacts with uranyl nitrate in MeOH under formation of (H₂APTSC)[UO₂(NO₃)₂(μ‐OH)]₂ ( 2 ) or [ UO₂(APTSC)(MeOH)(MeO)]₂ ( 3 ) depending on the experimental conditions applied. Protonation of 1 and precipitation of the [UO₂(NO₃)₂(μ‐OH)]₂^2— dianion as acetylpyridinium thiosemicarbazone salt is observed when the reaction is performed without the addition of a base. The metal atoms are situated in the centres of distorted hexagonal bipyramids. The U—U distance is 3.892(1)Å. Addition of triethylamine results in deprotonation of HAPTSC and the formation of 3 which is an unusual dimer with four methanol/methanolato ligands of two metal sites sharing two protons. The U—U distance in this dimer is 5.313(1)Å. (Bu₄N)[UO(APTSC)Cl₂] ( 4 ) is obtained when (Bu₄N)₂[UO₂Cl₄] is used as precursor. The uranium atoms in 3 and 4 are seven co‐ordinate. Their co‐ordination polyhedra can best be described as pentagonal bipyramids. Compounds 3 and 4 represent the first examples of thiosemicarbazone complexes with actinide elements which haven been studied by X‐ray analysis.     

Filling the equatorial garland of uranyl ion: its content and limitations

Crystal structure determinations on the uranyl ion complexes [H₂N(CH₃)₂]₂[UO₂(bpdc)₂], (1), (bpdc?=?2,2′-bipyridine-3,3′-dicarboxylate), [pyH]₂[UO₂(btfac)(NO₃)₂](NO₃), (2), (btfac?=?1-phenyl-4,4,4-trifluorobutane-1,3-dionate), [H₂dabco][UO₂(nta)]₂·3H₂O, (3), (dabco?=?1,4-diazabicyclo[2.2.2]octane; nta?=?nitrilotriacetate) and [Ni(cyclam)UO₂(edta)]^.2H₂O, (4), (cyclam?=?1,4,8,11-tetrazacyclotetradecane; edta?=?ethylenediaminetetraacetate) have provided further examples of U(VI) in tetragonal-, pentagonal and hexagonal-bipyramidal coordination environments. Consideration of each structure within the context of those of known relatives has been used to assess the influence of factors in addition to repulsions within the primary coordination sphere on the equatorial coordination number of U(VI).

     

Behavior of nitrite forms of nitrosylruthenium on extraction and back extraction of heterometalic Ru/Zn complexes with trioctylphosphine oxide

The state of ruthenium in conjugated phases upon extraction of trans-[Ru(¹⁵NO)(¹⁵NO₂)₄(OH)]^2? complex with tri-n-octylphosphine oxide (TOPO) in the presence of Zn²⁺ and subsequent back extraction with H¹⁵NO₃ and NH₃(concd.) solutions was studied by ¹⁵N NMR. Binuclear complexes [Ru(NO)(NO₂)_5?n (μ-NO₂) _n?1(μ-OH)Zn(TOPO) _n ] and [Ru(NO)(NO₂)_4?n (ONO)(μ-NO₂) _n?1(μ-OH)Zn(TOPO) _n ], where n = 2, 3, are predominant forms in extract. Kinetic restrictions for ruthenium extraction with TOPO solution in hexane and its back extraction with aqueous solutions of nitric acid and ammonia are eliminated in the absence of direct coordination of extractant to ruthenium. fac-Dinitronitrosyl forms [Ru(NO)(H₂O)₃(NO₂)₂]⁺, [Ru(NO)(H₂O)₂(NO₂)₂(NO₃)]⁰ (3 and 6 M HNO₃) and [Ru(NO)(H₂O)(NO₂)₂(NO₃)₂]^? (6 M HNO₃) prevail in nitric acid back extracts. Equilibrium constant at ambient temperature (0.05 ± 0.01) was assessed for the coordination of second nitrate ion to nitrosylruthenium dinitronitrato complex. Complex species [Ru(NO)(NO₂)₄(OH)]^2? and [Ru(NO)(NO₂)₃(ONO)(OH)]^2? prevail in ammonia back extract.     

Mixed-ligand complexes of paddlewheel dinuclear molybdenum as hydrodehalogenation catalysts for polyhaloalkanes

We developed a hydrodehalogenation reaction of polyhaloalkanes catalyzed by paddlewheel dimolybdenum complexes in combination with 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) as a non-toxic H-atom source as well as a salt-free reductant. A mixed-ligated dimolybdenum complex Mo₂(OAc)₂[CH(NAr)₂]₂ (3a, Ar = 4-MeOC₆H₄) having two acetates and two amidinates exhibited high catalytic activity in the presence of ⁿBu₄NCl, in which [ⁿBu₄N]₂[Mo₂{CH(NAr)₂}₂Cl₄] (9a), derived by treating 3a with ClSiMe₃ and ⁿBu₄NCl, was generated as a catalytically-active species in the hydrodehalogenation. All reaction processes, oxidation and reduction of the dimolybdenum complex, were clarified by control experiments, and the oxidized product, [ⁿBu₄N][Mo₂{CH(NAr)₂}₂Cl₄] (10a), was characterized by EPR and X-ray diffraction studies. Kinetic analysis of the hydrodehalogenation reaction as well as a deuterium-labelling experiment using MBTCD-d₈ suggested that the H-abstraction was the rate-determining step for the catalytic reaction.     

Reactions of tetrachlorodioxouranate(VI) ion with neutral and protic ligands

Summary The reactions of [bipyH₂][UO₂Cl₄]·3H₂O (bipyH₂=diprotonated 2,2-bipyridyl) with a series of neutral and protic oxygen donor ligands have been investigated. N,N-dimethyl formamide (DMF), N,N-dimethyl acetamide (DMA) and dimethyl sulphoxide (DMSO) gave compounds of the type [bipyH₂][UO₂Cl₄(L)₂] (L=DMF or DMA) and [bipyH₂][UO₂Cl₄(DMSO)_n] (DMSO)_3-n (n=1 or 2), while [bipyH₂][UO₂Cl₄-(3PNO)(DMSO)_n](DMSO)_2-n (n=1 or 2) and [bipyH][UO₂Cl₃(4PNO)(DMSO)] were obtained with 3-picoline N-oxide (3PNO) and 4-picoline N-oxide (4PNO) respectively from DMSO medium. With excess 2-picoline N-oxide (2PNO) the compound [bipyH][UO₂Cl₃(2PNO)](DMSO) was obtained. Reaction with acetyl acetone (AcAcH) and 8-hydroxy quinoline (QH) in 1:1 mole ratio in DMSO gave compounds of the type [bipyH₂][UO₂Cl₃(L)(DMSO)] (L=AcAc or Q). The compounds have been investigated by i.r. spectra, powder x-ray diffraction and molar conductivity measurements.     

Synthese und Kristallstrukturen von [Cu4(As4Ph4)2(PRR′2)4], [Cu14(AsPh)6(SCN)2(PEt2Ph)8], [Cu14(AsPh)6Cl2(PRR′2)8], [Cu12(AsPh)6(PPh3)6], [Cu10(AsPh)4Cl2(PMe3)8], [Cu12(AsSiMe3)6(PRR′2)6] und [Cu8(AsSiMe3)4(PtBu3)4] (R,R′ = organische Gruppen)

Syntheses and Crystal Structures of [Cu₄(As₄Ph₄)₂(PRR′₂)₄], [Cu₁₄(AsPh)₆(SCN)₂(PEt₂Ph)₈], [Cu₁₄(AsPh)₆Cl₂(PRR′₂)₈], [Cu₁₂(AsPh)₆(PPh₃)₆], [Cu₁₀(AsPh)₄Cl₂(PMe₃)₈], [Cu₁₂(AsSiMe₃)₆(PRR′₂)₆], and [Cu₈(AsSiMe₃)₄(P^tBu₃)₄] (R, R′ = Organic Groups) Through the reaction of CuSCN with AsPh(SiMe₃)₂ in the presence of tertiary phosphines the compounds [Cu₄(As₄Ph₄)₂(PRR′₂)₄] ( 1 – 3 ) ( 1 : R = R′ = ⁿPr, 2 : R = R′ = Et; 3 : R = Me, R′ = ⁿPr) and [Cu₁₄(AsPh)₆(SCN)₂(PEt₂Ph)₈] ( 4 ) can be synthesised. Using CuCl instead of CuSCN results to the cluster complexes [Cu₁₄(AsPh)₆Cl₂(PRR′₂)₈] ( 5–6 ) ( 5 : R = R′ = Et; 6 : R = Me, R′ = ⁿPr), [Cu₁₂(AsPh)₆(PPh₃)₆] ( 7 ) and [Cu₁₀(AsPh)₄Cl₂(PMe₃)₈] ( 8 ). Through reactions of CuOAc with As(SiMe₃)₃ in the presence of tertiary phosphines the compounds [Cu₁₂(AsSiMe₃)₆(PRR′₂)₆] ( 9 – 11 ) ( 9 : R = R′ = Et; 10 : R = Ph, R′ = Et; 11 : R = Et, R′ = Ph) and [Cu₈(AsSiMe₃)₄(P^tBu₃)₄] ( 12 ) can be obtained. In each case the products were characterised by single‐crystal‐X‐ray‐structure‐analyses. As the main structure element 1 – 3 each have two As₄Ph₄^2–‐chains as ligands. In contrast 4 – 12 contain discrete AsR^2–ligands.     

Chemie der carbonylniobverbindungen: X. Neue hydridocarbonylkomplexe des vanadiums,niobs und tantals

Complexes of the general formula HM(CO)_n(oligophos) (M = V, n = 2; M = Nb, n = 3 and 2; M = Ta, n = 3) have been prepared by ion exchange on silica gel from their ionic precursors [Et₄N][M(CO)_4,3(oligophos)] (n = 3) or by UV irradiation of HM(CO)_n+1(oligophos) (n = 2). The new compounds, including fac-[Et₄N]-[Nb(CO)₃PPh(CH₂CH₂PPh₂)₂] and cis-[Et₄N][Ta(CO)₄PPh(CH₂CH₂PPh₂)₂], are characterized by their IR (ν(CO)), ¹H (hydride), ³¹P and metal (⁵¹V and ⁹³Nb) NMR spectra.     

Beiträge zur Koordinationschemie von Rhenium(III)chlorid in nichtwäßrigen Lösungen

Coordination reactions of solutions of Re₃Cl₉ in acetonitrile, propanediol-1,2-carbonate, acetone and dimethylsulfoxide yield compounds with unchanged metal-cluster structures. The following compounds were isolated and characterised: [Et ₄N]₃[Re₃Cl₉(N₃)₃], [Et ₄N]₃[Re₃Cl₆(N₃)₆], [Et ₄N]₃[Re₃Cl₃(N₃)₉], [Et ₄N]₃[Re₃Cl₉(CN)₃], [Et ₄N]₃[Re₃Cl₃(CN)₉],Et ₄N]₃[Re₃Cl₉(NCS)₃], [Et ₄N]₃[Re₃Cl₆(NCS)₆], [Et ₄N]₃[Re₃Cl₃(NCS)₉], Re₃Cl₉·(DMSO)₃, Re₃Cl₉·(HMPT)₃.     

Synthesis and characterization of complexes of UO2(II) and Th(IV) of bis-schiff bases derived from furoylpyrazolone

Four new complexes of UO₂(II) and Th(IV) with bis-Schiff bases, derived from N,N'-bis[(l-phenyl-3-methyl-5-oxo-4-pyrazolinyl)-a-furylmethylidyne]-1,2-propylenediimine [1,2-BPMOPFP-H₂] and N,N'- bis[(l-phenyl-3-methyl-5-oxo-4-pyrazolinyl)-a-furylmethylidyne]-1,3-propylenediimine [1,3-BPMOPFP-H₂], were synthesized and characterized by elemental analysis, IR, UV, ¹HNMR spectroscopy, and molar conductivity. The general formula of the complexes was confirmed to be [UO₂(BPMOPFP)], [Th(BPMOPFP)(NO₃)]NO₃. A possible structure for the complexes have been proposed.     

Titanium ketimide complexes as α-olefin homo- and copolymerisation catalysts. X-ray diffraction structures of [TiCp(NCBu2)Cl2] (Cp=Ind, Cp*)

The synthesis of [TiInd(NC^tBu₂)Cl₂] and the applications of [TiCp^′(NC^tBu₂)Cl₂] (Cp^′=Ind, Cp*, Cp) as ethylene and propylene homopolymerisation catalysts, as well as its behaviour as catalysts of ethylene and 10-undecen-1-ol copolymerisation are described. The optimisation of the catalytic reactions showed that all compounds are very active homopolymerisation catalysts, particularly [TiInd(NC^tBu₂)Cl₂] that gives 123.37 × 10⁶ g/(molTi [E] h) and 50.77 × 10⁶ g/(molTi [P] h) of linear polyethylene and atatic polypropylene, respectively. The less active homopolymerisation catalyst, [TiCp(NC^tBu₂)Cl₂], is the most effective ethylene/10-undecen-1-ol copolymerisation catalyst, leading to the highest degree of polar monomer incorporation. The polymers obtained were characterised by NMR and DSC. The molecular structures of [TiCp^′(NC^tBu₂)Cl₂] (Cp^′=Ind, Cp*) were determined by X-ray diffraction studies.     

Organophosphonate derivatives of titanium and niobium alkoxoanions

The organophosphonate-substituted alkoxides [Bu₄ⁿN]₂[{Ti(OMe)₃(O₃PPh)}₂] (1) and [Bu₄ⁿN]₂[{Nb(OMe)₃(O₃PPh)}₂(μ-O)] (2) have been prepared from [Bu₄ⁿN][PhPO₃H] and the metal alkoxides Ti(OMe)₄ or Nb(OMe)₅ respectively. In 1, the bridging phenylphosphonates occupy trans coordination sites, whereas in 2, a cis–bridging geometry is adopted.     

Phase diagrams for the [Th(NO3)4(TBP)2]-decane-[UO2(NO3)2(TBP)2] liquid ternary system

We report a phase diagram (on the mole fraction scale) for the [Th(NO₃)₄(TBP)₂]-decane-[UO₂(NO₃)₂(TBP)₂](1-2-3) ternary liquid system, where TBP stands for tributyl phosphate, at T = 298.15 K. This system is characterized by a homogeneous solution field and a two-liquid field (immiscibility field); one phase (phase I) is enriched in [Th(NO₃)₄(TBP)₂] and [UO₂(NO₃)₂(TBP)₂], and the other (phase II) is enriched in decane. Molecular interaction parameters and excess Gibbs energies G ^ex were calculated for the binary systems and the ternary liquid system along the binodal curve proceeding from miscibility in the [Th(NO₃)₄(TBP)₂]-decane system and the ternary system and using equations of the NTRL model. For the ternary system, G ^ex > 0. G ^ex decreases in the following order of pairs of liquids: (1, 2) > (2, 3) > (1, 3).     

Uranyl(VI) and lanthanum(III) thio-diglycolamides complexes: Synthesis and structural studies involving nitrate complexation

New tri-functional ligands of the type R₂NCOCH₂SCH₂CONR₂ (where R = iso-propyl, n-butyl or iso-butyl) were prepared and characterized. The coordination chemistry of these ligands with uranyl and lanthanum(III) nitrates was studied by using the IR, ¹HNMR and elemental analysis methods. Structures for the compounds [UO₂(NO₃)₂(ⁱPr₂NCOCH₂SCH₂CONⁱPr₂)] [UO₂(NO₃)₂(ⁱBu₂NCOCH₂SCH₂CONⁱBu₂)], [La(NO₃)₃(ⁱPr₂NCOCH₂SCH₂CONⁱPr₂)₂] and [La(NO₃)₃(ⁱBu₂NCOCH₂SCH₂CONⁱBu₂)₂] were determined by single crystal X-ray diffraction. These structures show that the ligand acts as a bidentate chelating ligand and bonds through both the carbamoyl groups to the uranyl and lanthanum(III) nitrate groups. Solvent extraction studies show that the ligand can extract the uranyl ion from the nitric acid medium but does not show any ability to extract the americium (III) ion.     

Two Rare-Earth Molecular Ferroelectrics with High Curie Temperatures,Large Spontaneous Polarization,Switchable Second Harmonic Generation Effects,and Strong Photoluminescence

Smart multifunctional molecular ferroelectrics bearing high Curie temperatures and diverse excellent physical properties, such as second harmonic generation (SHG) responses, luminescence, and semiconductivity, among others, have significant applications but have seldom been documented. Herein, the rare-earth metals Nd and Pr are introduced into a simple molecular system (nBu₄N )₃[M(NO₃)_x(SCN)_y] (nBu₄N₌tetrabutyl ammonium, M=rare-earth metal, nBu=CH₃CH₂CH₂CH₂), and two new multifunctional molecular ferroelectrics are obtained: (nBu₄N )₃[Nd(NO₃)₄(SCN)₂] ( 1 ) and (nBu₄N )₃[Pr(NO₃)₄(SCN)₂] ( 2 ). Their distinct heat and dielectric anomaly dependence on temperature verifies that compounds 1 and 2 experience high-temperature para-ferroelectric phase transitions at 408 and 413 K, respectively. Strikingly, both molecular ferroelectrics possess large spontaneous polarization with P_s values of 9.05 and 8.50 μC cm⁻², respectively, and are further characterized by the appearance of multiple intersecting non-180° domains and polarization switching behavior. In particular, compounds 1 and 2 show good stability with only a small decrease in SHG intensity after switching cycles, suggesting that they have great potential for application in nonlinear optical (NLO) switches. Simultaneously, the rare-earth compounds 1 and 2 present bright yellow–red and bright green fluorescence, respectively, at room temperature.     

Phase equilibria at various temperatures in the ternary liquid system containing solvates of thorium(IV) and uranyl(VI) nitrates with tri-n-butyl phosphate and tetradecane

The phase diagram of the ternary liquid system [Th(NO₃)₄(TBP)₂]-[UO₂(NO₃)₂(TBP)₂]-tetradecane (where TBP stands for tri-n-butyl phosphate) has been investigated at temperatures from 298.15 to 333.15 K. The ternary liquid system is characterized by a region of homogeneous solutions and a region of two-phase liquid systems (stratified systems). One phase is enriched with solvates [Th(NO₃)₄(TBP)₃] and [UO₂(NO₃)₂(TBP)₂] (phase I), and the other is enriched with tetradecane (phase II). The temperature (T = 298.15–333.15 K) does not substantially affect the two-phase region. In the two-phase systems, the preferential distribution of [UO₂(NO₃)₂(TBP)₂] into phase I is observed in spite of the fact that the binary system [UO₂(NO₃)₂(TBP)₂]-tetradecane is a single phase at all temperatures investigated. The distribution of [UO₂(NO₃)₂(TBP)₂] into phase I leads to the redistribution of [Th(NO₃)₄(TBP)₂] into phase II. At all temperatures investigated, the critical solution points of the ternary liquid system have compositions with close contents of the solvates [Th(NO₃)₄(TBP)₂] and [UO₂(NO₃)₂(TBP)₂].