Syntheses and Crystal Structures of Potassium–Lanthanoid(III) Complexes with the 1,2‐Benzenedisulfonate Ligand

The complexes [K(H₂O)₂LnL₂] (Ln = La or Nd; L = 1,2‐benzenedisulfonate) and [K(H₂O)Yb(H₂O)₄L₂] were initially isolated fortuitously from attempts to prepare the corresponding Ln₂L₃ complexes from Ln₂O₃ and H₂L in water. Indeed the bulk products from these reactions have the composition Ln₂L₃. Subsequently, deliberate syntheses by reacting equimolar amounts of Ln₂L₃ with K₂L in water gave the complexes in good yield. X‐ray crystal structures of [K(H₂O)₂LnL₂] (Ln = La or Nd) showed the complexes to be isostructural with a two dimensional polymeric network structure in which LnL₂ units are linked into chains crosslinked by potassium ions. Each Ln is nine coordinate with solely sulfonate oxygen donor atoms. Between adjacent lanthanoid ions there are three different types of sulfonate bridges and two examples of each. Most noteworthy is highly unsymmetrical bridging through μ‐η²‐sulfonate oxygen atoms. Consequently, one Ln–O bond is ca. 0.5 Å longer than the other eight. Potassium is nine‐coordinate with seven sulfonate oxygen atoms and two aqua ligands, and surprisingly <K–O(sulfonate)> is much longer than <K–O(H₂O)>. Pairs of potassium ions are linked by two μ‐η²‐sulfonate oxygen atoms, which are unsymmetrically bridging. The structure of [K(H₂O)Yb(H₂O)₄L₂] comprises discrete tetranuclear units containing two independent ytterbium ions, each coordinated by four water molecules and two chelating (via seven membered rings) disulfonate ligands, and two potassium ions, each coordinated by six sulfonate oxygen atoms and a water molecule. For each potassium, four of the coordinated sulfonate oxygen atoms are from sulfonate ligands bonded to one ytterbium atom and two from sulfonate ligands attached to the other ytterbium atom. In contrast to the Nd and La complexes, <K–O(sulfonate)> is shorter than <K–O(H₂O)>.     

Synthesis and Characterization of Bis(pyridylimino)isoindolide Alkali Metal Complexes in Three Redox States

Non-innocent ligands (NILs) like bis(pyridylimino)isoindolide (BPI) play crucial roles in coordination chemistry, biosciences, catalysis and material sciences. Investigating the isolated redox states of NILs is inevitable for understanding their redox-activity and fine-tuning the properties of corresponding metal complexes. The limited number of fundamental studies on the coordination behavior and redox chemistry of reduced BPI species is suggested to hamper further applications of the title compounds. This work describes for the first time the isolation of alkali metal complexes of BPI and Me₂BPI in three different oxidation states and their characterization by means of NMR or EPR spectroscopy, DFT calculations, and SC-XRD studies. The latter revealed the connection between bond orders in the ligand scaffold and its oxidation state. The paramagnetic compound Me₂BPI-K₂ was isolated as a coordination copolymer with 18-crown-6, which enabled the characterization of the dianionic BPI radical. Furthermore, the so-far unknown trianionic state of BPI was reported by the isolation of BPI-K₃. This divulges an unprecedented bis(amidinato)isoindolide coordination mode.     

Synthesis and Structures of Homoleptic Monomeric Potassium Aryloxolanthanoidate(III) Complexes

Reaction of lanthanoid tris(2, 6‐diphenylphenolates) [Ln(Odpp)₃] with KOdpp in 1, 2, 4, 5‐tetramethylbenzene (durene) at 200‐250 °C affords [K{Ln(OC₆H₃Ph₂‐2, 6)₄}], (Ln = La ( 1 ) or Nd ( 2 )) and 2 has also been obtained from the reaction of [Nd(Odpp)₃] with potassium hydride. In the solid state, 1 and 2 are monomeric bimetallics in which Ln is surrounded by a distorted tetrahedral array of oxygen atoms. Two Odpp ligands are oxygen bridged between K and Ln and also are η⁴‐Ph linked to potassium. One Odpp ligand bridges the metals in an O(Ln): η⁶‐Ph(K) manner that is new for lanthanoid complexes of this ligand, with no close K‐O contact, and the remaining Odpp is terminal on the Ln.     

The Synthesis and Spectroscopic Characterization of Heterobimetallic Bu2Sn(IV) Complexes Derived from Some Chelating Ligands

The interaction of Bu₂Sn(OPrⁱ)₂ with a trifunctional tetradentate Schiff base (LH₃) (where H₃L = HOC₆H₄CH═NCH₃C(CH₂OH)₂) yields the precursor complex Bu₂Sn(LH) 1, which, on equimolar reactions with different metal alkoxides [Al(OPrⁱ)₃, Bu₃Sn(OPrⁱ), Ge(OEt)₄]; Al(Medea)(OPrⁱ) (where Medea = CH₃N- (CH₂CH₂O)₂); and Me₃SiCl in the presence of Et₃N], affords, respectively, the complexes Bu₂Sn(L)Al(OPrⁱ)₂ 2, Bu₂Sn(L)Al(Medea) 3, Bu₂Sn(L)Bu₃Sn 4, Bu₂Sn(L)Ge(OEt)₃ 5, and Bu₂Sn(L)SiMe₃ 6. The reactions of 2 with 2,5-dimethyl-2,5-hexanediol in a 1:1 ratio and with acetylacetone (acacH) in a 1:2 molar ratio afforded derivatives Bu₂Sn(L)Al(OC(CH₃)₂CH₂CH₂C(CH₃)₂ O) 7 and Bu₂Sn(L)Al(acac)₂ 8, respectively. All of the derivatives 1– 8 have been characterized by elemental analyses, molecular weight measurements, and spectroscopic [IR and NMR (¹H, ¹¹⁹Sn, ²⁹Si, and ²⁷Al)] studies.     

异金属配合物的合成、表征与光谱性质

以多氨羧酸为配体,在水溶液中合成了两个同时含Bi3+和Eu3+两种金属的晶态配合物BiEu(edta)(NO3)2·6.5H2O和非晶态配合物BiEu(dtpa)(NO3)·4(H2O).采用元素分析仪、红外光谱仪、X射线粉末衍射仪等手段对产物进行表征.采用热分析仪对产物的热稳定性进行了研究.室温下采用紫外可见光度计和荧光光谱仪对固态产物的光学性质进行测试,结果显示产物既发Eu3+的线状特征荧光,又发Bi3+的带状荧光.     

Bis(2-pyridylimino)isoindole (BPI) Ligands with Novel Linker Units: Synthesis and Characterization of Their Palladium and Platinum Complexes

Summary. With the aim of immobilizing bis(2-pyridylimino)isoindolate (BPI) ligands their backbone structure has been functionalized with several linker units. Their fixation was carried out at the stage of the phthalodinitrile precursor by nucleophilic ipso-substitution of 4-nitrophthalodinitrile. Subsequent synthesis of the functionalized phthalodinitriles with two molar equivalents of the 2-aminopyridine derivatives gave the corresponding BPI ligands. Reaction of the ethyleneglycol functionalized BPI derivative with the zeroth generation carbosilane dendrimer [G-0]_4-exo-Cl yielded the functionalized dendrimer [G-0]_4-exo-[O(CH₂)₂O]-10-MeBPI (7). The synthesis of the palladium complexes was carried out by reaction of the protioligands with [(PhCN)₂PdCl₂] in benzene using triethylamine as auxiliary base whereas the first examples of BPI-platinum complexes were prepared using [(COD)PtCl₂] as starting material.     

Sc3+ Chloro and Alkyl Complexes Coordinated by Pincer NHC-Tethered Bis(phenolate) Ligands

Bis(phenolate) ligands with benzimidazole-2-ylidene ( L¹) and tetrahydropyrimidine-2-ylidene ( L² ) linkers proved to be suitable coordination environments for the synthesis of isolable Sc³⁺ chloro and alkyl complexes. The treatment of Sc(CH₂SiMe₃)₃(THF)₂ with equimolar amounts of [ L^1,2H₃ ] Cl afforded chloro complexes L^1,2ScCl ( solv ) ₂ (solv=THF, Py) in 76–85 % yields. L^1,2ScCl ( THF ) ₂ were also prepared by the salt metathesis reactions of ScCl₃ with [ L^1,2 ] Na₂ generated from [ L^1,2H₃ ] Cl and 3 equiv. of NaN(SiMe₃)₂ (−40 °C, THF) and isolated in somewhat lower yields (68–73 %). L²ScCl ( THF ) ₂ was subjected to the alkylation reaction with LiCH₂SiMe₃ affording alkyl derivative [ L²Sc ( CH₂SiMe₃ )] ₂ . This compound can be alternatively prepared by the subsequent reactions of [ L²H₃ ] Cl with equimolar amount of NaN(SiMe₃)₂ and Sc(CH₂SiMe₃)₃(THF)₂. In the dimeric alkyl compound [ L²Sc ( CH₂SiMe₃ )] ₂ , one of the phenoxide groups of the dianionic ligand is coordinated to one scandium center, while the second one features μ-bridging coordination with two metal centers.     

Template‐Directed Self‐Recognition of Alkyl‐Bridged Bis(catechol) Ligands in the Formation of Helicate‐Type Complexes

A controlling influence on the self‐assembly in the complexation reaction of a mixture of methylene‐ and ethylene‐bridged bis(catechol) ligands ( 1 ‐H₄ and 2 ‐H₄, respectively) with titanium(IV ) ions is exerted by alkali metal cations (see scheme). Thus, not a complicated mixture of complexes, but as a result of a self‐recognition of the ligands only well‐defined products are formed.     

Synthesis, Characterization and Structural Properties of Some Heterobimetallic Carbonyl Clusters Derived from Diethynylsilane and Diethynyldisilane Ligands

We report the synthesis of some heterobimetallic carbonyl clusters of groups 8 and 9 derived from diethynylsilane and diethynyldisilane ligands. The triosmium carbonyl clusters containing a pendant acetylene unit [(μ-CO)Os₃(CO)₉(μ₃-η²-HC≡C-E-C≡CH)] [E = Si(CH₃)₂, Si(CH₃)₂–Si(CH₃)₂ and SiPh₂] were prepared and subsequently used for mixed-metal cluster formation. New diyne complexes of the type [{(μ-CO)Os₃(CO)₉}{Co₂(CO)₆}(μ₃-η²:η²-diyne)] and [{(μ-CO)Os₃(CO)₉}{(μ-H)Ru₃(CO)₉}(μ₃-η²:μ₃-η², η²-diyne)] [diyne = HC≡CSi(CH₃)₂C≡CH, HC≡CSi(CH₃)₂–Si(CH₃)₂C≡CH or HC≡CSi(Ph)₂C≡CH] have been prepared in good yields from the reaction of [(μ-CO)Os₃(CO)₉(μ₃-η²-HC≡C-E-C≡CH)] with a molar equivalent of [Co₂(CO)₈] and [Ru₃(CO)₁₂], respectively. All the new heterobimetallic compounds have been characterized by IR and ¹H NMR spectroscopy and mass spectrometry. The X-ray crystal structures and computational analyses based on density functional theory of these three molecules have been studied. Structurally, the dicobalt species adopts a pseudo-tetrahedral Co₂C₂ core with the alkyne bond which lies essentially perpendicular to the Co–Co vector. For the mixed osmium–ruthenium analogue, the hexanuclear carbonyl cluster consist of two trinuclear metal cores with the μ₃-(η²-||) bonding mode for the acetylene group in the former case and the μ₃-η², η² bonding mode in the latter one.     

Synthesis and Characterization of Novel Lanthanocene Complexes with Dichalcogenolate o-Carboranyl Ligands

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Synthesis of Heterobimetallic Phosphido-Bridged W-Mo Complexes with Chelating dppe and dppm Ligands

Reactions between and bidentate phosphines (dppm and dppe) produced complexes and with chelating dppm and dppe ligands as only products. No bridging bidentate phosphine complex was observed. Both complexes were spectroscopically characterized.     

Heteroleptic Lanthanide Complexes with Aryloxide Ligands. Synthesis and Structural Characterization of Divalent and Trivalent Samarium Aryloxide/Halide and Aryloxide/Cyclopentadienide Complexes

Synthesis of a new class of heteroleptic samarium aryloxide complexes has been achieved by the use of homoleptic samarium(II) bis(aryloxide) Sm(OAr)(2)(THF)(3) (1, Ar = C(6)H(2)Bu(t)(2)-2,6-Me-4) as a starting material, which is easily obtained by reaction of Sm(N(SiMe(3))(2))(2)(THF)(2) with 2 equiv of ArOH in THF. 1 reacts with 1 equiv of SmI(2) in THF to give Sm(II) mixed aryloxide/iodide [(ArO)Sm(&mgr;-I)(THF)(3)](2) (2), which adopts a dimeric structure via very weak Sm.I (3.534(2) ?) interactions. Reaction of 2 with C(5)Me(5)K in THF/HMPA affords the corresponding Sm(II) aryloxide/cyclopentadienide (C(5)Me(5))Sm(OAr)(HMPA)(2) (3). Oxidation of 1 with 0.5 equiv of I(2) in THF gives monomeric samarium(III) aryloxide/iodide (ArO)(2)SmI(THF)(2) (4), while the similar reaction of 1 with ClCH(2)CH(2)Cl or (t)BuCl in THF affords dimeric samarium(III) aryloxide/chloride [(ArO)(2)Sm(&mgr;-Cl)(THF)](2) (5). Crystal data for 1: monoclinic, space group P2(1), a = 9.903(3) ?, b = 16.718(5) ?, c = 13.267(2) ?, beta = 95.17(2) degrees, V = 2187(2) ?(3), Z = 2, D(c) = 1.223 g cm(-)(3), R = 0.0634. Crystal data for 2.2THF: monoclinic, space group P2(1)/a, a = 18.330(6) ?, b = 14.320(4) ?, c = 13.949(3) ?, beta = 103.16(2) degrees, V = 3563(2) ?(3), Z = 2, D(c) = 1.46 g cm(-)(3), R = 0.0606. Crystal data for 3: triclinic, space group P&onemacr;, a = 10.528(1) ?, b = 12.335(2) ?, c = 19.260(2) ?, alpha = 101.33(1) degrees, beta = 95.230(9) degrees, gamma = 108.54(1) degrees, V = 2293.1(5) ?(3), Z = 2, D(c) = 1.25 g cm(-)(3), R = 0.0358. Crystal data for 4: monoclinic, space group C2/c, a = 17.191(7) ?, b = 10.737(6) ?, c = 21.773(7) ?, beta = 98.80(3) degrees, V = 3971(3) ?(3), Z = 4, D(c) = 1.44 g cm(-)(3), R = 0.0467. Crystal data for 5: monoclinic, space group P2(1)/n, a = 13.750(3) ?, b = 17.231(3) ?, c = 14.973(6) ?, beta = 95.81(2) degrees, V = 3529(2) ?(3), Z = 2, D(c) = 1.31 g cm(-)(3), R = 0.0557.     

二（胍基）锆配合物的合成和表征

Addition of one equivalent of LiN（i-Pr）2 or LiN（CH2）5 to carbodiimides, RN=C=NR [R=cyclohexyl （Cy）, isopropyl （i-Pr）], generated the corresponding lithium of tetrasubstituted guanidinates {Li[RNC（N R^′2）NR]（THF）}2 [R=i-Pr, N R^′2=N（i-Pr）2 （1）, N（CH2）5 （2）; R=Cy, N R^′2=N（i-Pr）2 （3）, N（CH2）5 （4）]. Treatment of ZrCl4 with freshly prepared solutions of their lithium guanidinates provided a series of bis（guanidinate） complexes of Zr with the general formula Zr[RNC（N R^′2）NR]2Cl2 [R=i-Pr, N R^′2=N（i-Pr）2 （5）, N（CH2）5 （6）; R=Cy, N R^′2=N（i-Pr）2 （7）, N（CH2）5 （8）]. Complexes 1, 2, 5-8 were characterized by elemental analysis, IR and ^1H NMR spectra. The molecular structures of complexes 1, 7 and 8 were further determined by X-ray diffraction studies.     

Synthesis and Characterization of Novel Orange-emitting Iridium(III) Complexes with Diphenylquinoline Ligands Containing Fluorinated Substituent

Recently, the iridium complexes as phosphorescent emitter in organic light-emitting diodes (OLEDs) have attracted much attention since the realization of a high efficiency OLED device based on the complex fac tris(2-phenylpyridine)iridium [Ir(ppy)3]1-4. T…     

Schiff碱双冠醚和稀土硝酸盐配位行为的研究

迄今为止,研究稀土冠醚配合物所用的配体都是分子中含一个冠醚环的单冠醚化合物,配体中含有两个冠醚环的双冠醚稀土配合物还未见到报道。Handside于1982年报道了一系列结构式为右边所示的Schiff碱双冠醚。本文报道m=2,n=2的Schiff     

Synthesis and Structural Characterization of two Novel Copper(I) Complexes with Oxygen Donor

Two novel copper(I) complexes with Cu‐O bonds, [Cu₂L₂(PPh₃)₂](BF₄)₂ ( 1 ) and [Cu(L)(dppeo)](BF₄) ( 2 ) ( L = 6‐(4‐diethylmethylphosphonatephenyl)‐2,2′‐bipyridine, dppeo = bis(diphenylphosphino)ethane monoxide), have been prepared and their structures characterized. In the binuclear complex 1 , the ligand L serves as tridentate donor with the N, N′ and O as coordination atoms, and the two Cu^I atoms are bridged through both P = O donor atoms in different ligand L with a triphenylphosphine molecule as auxiliary ligand. While in mononuclear complex 2 , both ligands L and dppeo behave as bidentate with N^∧N from L and P^∧O from dppeo chelating to Cu^I atom.     

新型硅基桥连双(环戊二烯基)四羰基二铁类配合物的合成

以六甲基二硅烷为原料,经氯代、格式反应和锂化反应制得双(环戊二烯基)配体(C5H5)2MeSiSiMe2R(3a^3c),将该配体分别与五羰基铁在对二甲苯中回流反应,合成了3种新型的硅基桥连双(环戊二烯基)四羰基二铁类配合物[η^5,η^5-C5H4MeSi(SiMe2R)C5H4]Fe2(CO)2(μ-CO)2[R=p-C6H4CH3(4a),R=p-C6H4OCH3(4b),R=CH2C6H5(4c)],其结构经1H NMR,13C NMR,IR和元素分析表征。并用X-射线单晶衍射法确定了配合物4b的分子结构。结果表明:4b(CCDC:1942618)属单斜晶系,Cc空间群,晶胞参数a=18.591(3)A,b=10.3080(10)A,c=14.136(2)A,α=90°,β=117.262(6)°,γ=90°,V=2408.1(6)A^3,Z=4,F(000)=1152,Dc=1.546 g·cm^-3,μ=1.338 mm^-1,R1=0.0351,wR2=0.0754。     

Structural and Antimicrobial Studies of Some Divalent Transition Metal Complexes with Some New Symmetrical Bis (7-Formylanil Substituted-Sulfoxine) Schiff Base Ligands

Symmetrical bis (7-formyanil substituted-8-hydroxyquinoline-5-sulfonic acid), Schiff bases, react with Co(II), Ni(II) and Cu(II) ions to give M_nL (n=1, 2) complexes as established by conductometric titration in 1 : 1 DMF: H₂O. The complexes were identified by elemental analyses, molecular weight determination, thermal analysis, infrared, magnetic moments, electronic absorption, and electron spin resonance spectra. The suggested general geometry for these complexes may have a tetrahedral crystal structure and the general formula is [M₂L(OH₂4], where M(II) = Co, Ni and Cu and L = 7―X―H₂ L(―X―= dimethyl, p-phenyl, o-phenyl), while for the, trimethyl, ligand and the tetrahedral crystal structure has the general formula [M₂L(OH₂)₂].Antimicrobial activity of these ligands and their transition metal complexes has been investigated on some common fungi and bacteria. A considerable increase in the biocide acticity of these ligands has been observed on coordination with transition metal ions, therefore, these complexes can be used in the chemotherapy of candidiaces and other fungal skin diseases.     

Synthesis and Characterization of Bis(undeca-tungstoferrate) Lanthanates of Potassium

A series of novel rare earth complexes with 11-tungstoferrate as ligand, K15Ln(FeW11 O39)2 .xH2O(Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er or Yb) were prepared and characterized by elemental analyses, IR, UV-vis, polarograms, magnetic susceptibility and thermal measurement.Keywords Heteropoly complex, Rare earth complex, Synthesis, Bis(undecatungstoferrate) lanthanates of potassium