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1.
The reaction of [Ti(2)(micro-Cl)(2)(thf)(2)(eta-C(8)H(8))(2)] with Na[HB(mt)(3)] (mt = methimazolyl) provides the unusual salt [Ti{HB(mt)(3)}(2)][TiCl(4)(thf)(2)], the cation of which features homoleptic Ti(III)S(6) coordination. 相似文献
2.
Deng S Schwarzmaier C Eichhorn C Scherer O Wolmershäuser G Zabel M Scheer M 《Chemical communications (Cambridge, England)》2008,(34):4064-4066
A novel 1,2,3-triphosphaferrocene has been synthesised, which reacts with CuBr to give a 2D polymer, revealing an unprecedented pi-stacking of the triphospholyl moieties. 相似文献
3.
Rheingold AL Liable-Sands LM Golen JA Yap GP Trofimenko S 《Dalton transactions (Cambridge, England : 2003)》2004,(4):598-604
The new ligand, hydrotris[3-(diphenylmethyl)pyrazol-1-yl]borate, Tp(CHPh2), has been synthesized and its coordination chemistry was compared with that of the analogous Tp(iPr). The new ligand was converted to a variety of complexes, such as M[Tp(CHPh2)]X (M = Co, Ni, Zn; X = Cl, NCO, NCS), Pd[Tp(CHPh2)][eta3-methallyl], Co[Tp(CHPh2)](acac), and Co[Tp(CHPh2)](scorpionate ligand). Compounds Tl[Tp(CHPh2)], 1, Co[Tp(CHPh2)]Cl, 2, Co[Tp(CHPh2)](NCS)(DMF), 3, Ni[Tp(CHPh2)](NCS)(DMF)2, 4, Co[Tp(CHPh2)](acac), 5, Co[Tp(CHPh2)][Ph2Bp], 6, Co[Tp(CHPh2)][Bp(Ph)], 7, Co[Tp(CHPh2)][Tp], 8, and (Ni[Tp(CHPh2)])2[C2O4](H2O)2, 9, were structurally characterized. 相似文献
4.
Joy Chakraborty Santarupa Thakurta Brajagopal Samanta Aurkie Ray G. Pilet Stuart R. Batten Paul Jensen Samiran Mitra 《Polyhedron》2007
Three novel Schiff base Cd(II) trimeric complexes, [Cd3(L1)2(SCN)2(CF3COO)2] (1), [Cd3(L1)2(SCN)2(HCONMe2)] (2) and [Cd3(L2)2{N(CN)2}2] (3) have been prepared from two different symmetrical Schiff bases H2L1 and H2L2 (where H2L1 = N1,N3-bis(salicylideneimino)diethylenetriamine, a potentially pentadentate Schiff base with a N3O2 donor set, and H2L2 = N1,N3-bis(3-methoxysalicylideneimino)diethylenetriamine, a potentially heptadentate Schiff base with a N3O4 donor set). All the complexes have been synthesised under similar synthetic procedures and their crystal structures have been established by single crystal X-ray diffraction methods. The ligands and their metal complexes have been characterised by analytical and spectroscopic techniques. Among the three complexes, 1 and 3 are linear whereas 2 is a cyclic trimer. In 1 and 3, all the doubly phenoxo bridged Cd(II) metal centres are in a distorted octahedral environment. In complex 2, two of the three Cd(II) centres reside in a distorted octahedral environment and the remaining one enjoys a monocapped octahedral geometry. Altogether the variety in the bridging mode of two new salen-type ligands has been established through these complexes. 相似文献
5.
Masaaki Nabika Seiki Kiuchi Tatsuya Miyatake Kiyoshi Fujisawa 《Journal of polymer science. Part A, Polymer chemistry》2009,47(21):5720-5727
Manganese(II) complex catalysts with hydrotris(pyrazolyl)borate ligands have been examined on their catalytic performance in ethylene polymerization and ethylene/1‐hexene copolymerization. The activities of [Mn(L6)(Cl)(NCMe)] ( 1 ) and [Mn(L10)(Cl)] ( 2 ) activated by Al(i‐Bu)3/[Ph3C][B(C6F5)4] for ethylene polymerization go up to 326 and 11 kg mol (cat?1) h?1, respectively, (L6? = hydrotris(3‐phenyl‐5‐methyl‐1‐pyrazolyl)borate anion, L10? = hydrotris(3‐adamantyl‐5‐isopropyl‐1‐pyrazolyl)borate anion). In particular, for ethylene/1‐hexene copolymerization, complex 1 gives high‐molecular‐weight poly(ethylene‐co‐1‐hexene)s with the highest Mw of 439,000 in manganese olefin polymerization catalyst systems. Moreover, the 1‐hexene incorporation by complex 1 seems more efficient than that by [Mn(L3)(Cl)] ( 4 ) (L3? = hydrotris(3‐tertiary butyl‐5‐isopropyl‐1‐pyrazolyl)borate anion). In this work, we demonstrated that the coordination geometry and coordination number are also important factors for ethylene polymerization reaction as well as steric hindrances and ligand frameworks in our manganese(II) catalysts. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5720–5727, 2009 相似文献
6.
Fujisawa K Ono T Ishikawa Y Amir N Miyashita Y Okamoto K Lehnert N 《Inorganic chemistry》2006,45(4):1698-1713
Copper(I) complexes with tripodal nitrogen-containing neutral ligands such as tris(3,5-diisopropyl-1-pyrazolyl)methane (L1') and tris(3-tertiary-butyl-5-isopropyl-1-pyrazolyl)methane (L3'), and with corresponding anionic ligands such as hydrotris(3,5-diisopropyl-1-pyrazolyl)borate (L1-) and hydrotris(3-tertiary-butyl-5-isopropyl-1-pyrazolyl)borate (L3-) were synthesized and structurally characterized. Copper(I) complexes [Cu(L1')Cl] (1), [Cu(L1')(OClO3)] (2), [Cu(L1')(NCMe)](PF6) (3a), [Cu(L1')(NCMe)](ClO4) (3b), [Cu(L1')(CO)](PF6) (4a), and [Cu(L1')(CO)](ClO4) (4b) were prepared using the ligand L1'. Copper(I) complexes [Cu(L3')Cl] (5) and [Cu(L3')(NCMe)](PF6) (6) with the ligand L3' were also synthesized. Copper(I) complexes [Cu(L1)(NCMe)] (7) and [Cu(L1)(CO)] (8) were prepared using the anionic ligand L1-. Finally, copper(I) complexes with anionic ligand L3- and acetonitrile (9) and carbon monoxide (10) were synthesized. The complexes obtained were fully characterized by IR, far-IR, 1H NMR, and 13C NMR spectroscopy. The structures of both ligands, L1' and L3', and of complexes 1, 2, 3a, 3b, 4a, 4b, 5, 6, 7, and 10 were determined by X-ray crystallography. The effects of the differences in (a) the fourth ligand and the counteranion, (b) the steric hindrance at the third position of the pyrazolyl rings, and most importantly, (c) the charge of the N3 type ligands, on the structures, spectroscopic properties, and reactivities of the copper(I) complexes are discussed. The observed differences in the reactivities toward O2 of the copper(I) acetonitrile complexes are traced back to differences in the oxidation potentials determined by cyclic voltammetry. A special focus is set on the carbonyl complexes, where the 13C NMR and vibrational data are presented. Density functional theory (DFT) calculations are used to shed light on the differences in CO bonding in the compounds with neutral and anionic N3 ligands. In correlation with the vibrational and electrochemical data of these complexes, it is demonstrated that the C-O stretching vibration is a sensitive probe for the "electron richness" of copper(I) in these compounds. 相似文献
7.
Chahra Bouchameni Chahrazed Beghidja Adel Beghidja Pierre Rabu Richard Welter 《Polyhedron》2011,30(11):1774-1778
Two new complexes [MnIII(HL)2(acac)] and [MnII(HL)2]n have been obtained by reacting manganese(III) acetylacetonate monohydrate or manganese(II) chloride monohydrate with 2-salicylichydrazono-1,3-dithiolane ligand (H2L). Both compounds have been fully characterized by spectroscopic methods and single crystal X-ray diffraction. In the solid state, the molecular packing are described and discussed in term of weak H-bonds and short contacts. The unprecedented bridging coordination mode of this ligand lead to the first 2-salicylichydrazono-1,3-dithiolane-bridged coordination polymer [MnII(HL)2]n. The EPR spectrum of this compound was obtained with g ≈ 2.07, corresponding to a manganese ion (+II) in octahedral high-spin coordination sphere. The MnII complex exhibit paramagnetic behavior corresponding to quasi-isolated metal centers. 相似文献
8.
Marcelo P. Gil 《Journal of organometallic chemistry》2004,689(2):286-292
The synthesis, characterization and ethylene polymerization behavior of a set of Tp′MCl3 complexes (4, M=Ti, Tp′=HB(3-neopentyl-pyrazolyl)3−(TpNp); 5, M=Ti, Tp′=HB(3-tert-butyl-pyrazolyl)3−(TptBu); 6, M = Ti, Tp′=HB(3-phenyl-pyrazolyl)3−(TpPh); 7, M=Zr, Tp′=HB(3-phenyl-pyrazolyl)3−(TpPh); 8, M=Zr, Tp′ = HB(3-tert-butyl-pyrazolyl)3−(TptBu)) is described. Treatment of these tris(pyrazolyl)borate Group IV compounds with methylalumoxane (MAO) generates active catalysts for ethylene polymerization. For the polymerization reactions performed in toluene at 60 °C and 3 atm of ethylene pressure, the activities varied between 1.3 and 5.1 × 103 g of PE/mol[M] · h. The highest activity is reached using more sterically open catalyst precursor 4. The viscosity-average molecular weights () of the PE’s produced with these catalyst precursors varying from 3.57 to 20.23 × 105 g mol−1 with melting temperatures in the range of 127-134 °C. Further polymerization studies employing 7 varying Al/Zr molar ratio and temperature of polymerization showed that the activity as well as the polymer properties are dependent on these parameters. In that case, higher activity was attained at 60 °C. The viscosity-average molecular weights of the polyethylene’s decreases with increasing Al/Zr molar ratio. 相似文献
9.
Lehnert N Cornelissen U Neese F Ono T Noguchi Y Okamoto K Fujisawa K 《Inorganic chemistry》2007,46(10):3916-3933
This study focuses on the geometric (molecular) structures, spectroscopic properties, and electronic structures of copper(II)-nitrito complexes as a function of second coordination sphere effects using a set of closely related coligands. With anionic hydrotris(pyrazolyl)borate ligands, one nitrite is bound to copper(II). Depending on the steric demand of the coligand, the coordination mode is either symmetric or asymmetric bidentate, which leads to different ground states of the resulting complexes as evident from EPR spectroscopy. The vibrational spectra of these compounds are assigned using isotope substitution and DFT calculations. The results demonstrate that nu sym(N-O) occurs at higher energy than nu asym(N-O), which is different from the literature assignments for related compounds. UV-vis absorption and MCD spectra are presented and analyzed with the help of TD-DFT calculations. The principal binding modes of nitrite to Cu(II) and Cu(I) are also investigated applying DFT. Using a neutral tris(pyrazolyl)methane ligand, two nitrite ligands are bound to copper. In this case, a very unusual binding mode is observed where one nitrite is eta1-O and the other one is eta1-N bound. This allows to study the properties of coordinated nitrite as a function of binding mode in one complex. The N-coordination mode is easily identified from vibrational spectroscopy, where N-bound nitrite shows a large shift of nu asym(N-O) to >1400 cm-1, which is a unique spectroscopic feature. The optical spectra of this compound exhibit an intense band around 300 nm, which might be attributable to a nitrite to Cu(II) CT transition. Finally, using a bidentate neutral bis(pyrazolyl)methane ligand, two eta1-O coordinated nitrite ligands are observed. The vibrational and optical (UV-vis and MCD) spectra of this compound are presented and analyzed. 相似文献
10.
Néstor Novoa Vincent Dorcet Sourisak Sinbandhit Carolina Manzur 《Journal of Coordination Chemistry》2014,67(23-24):4101-4113
The tridentate ONO-donor Schiff base ligand derived from the condensation of 1-ferrocenyl-1,3-butanedione and 2-aminophenol, generated in situ and treated further with potassium tert-butoxide, reacted in THF with Co(NO3)2·6H2O in the presence of pyridine to afford the ionic complex [{(η5-C5H5)Fe(η5-C5H4)-C(O)CH=C(CH3)N-C6H4-2-O}2Co(III)]-[K(HOCH2CH3)2]+ (1, 50% yield). Compound 1 was characterized by elemental analysis, FT-IR, and multidimensional 1H and 13C NMR spectroscopy. Single-crystal X-ray diffraction reveals that the two metalloligands are meridionally coordinated to a Co(III) ion that adopts a slightly distorted octahedral geometry. The doubly solvated potassium counter-ion is asymmetrically positioned with respect to the two metalloligands. Such an arrangement allows the observation by 1H NMR of restricted rotation of the ferrocenyl units and the splitting of both carbonyl and imine carbons, thus suggesting that the structure observed in the solid state is retained in solution. Complex 1 exhibits in its cyclic voltammetry curve two anodic reversible waves attributed to the oxidation of Co(III)-phenolates into Co(III)-phenoxyl radical and that of the ferrocenyl fragment into its ferrocenium counterpart. 相似文献
11.
2-chloro-1,3,2-diazastibolenes react with Lewis acids either via Sb-Cl cleavage to yield stable Sb-analogues of an N-heterocyclic carbene, or via an unprecedented oxidative fragmentation to give a diazadiene-SbCl3 complex. 相似文献
12.
Christian P Rajaraman G Harrison A Helliwell M McDouall JJ Raftery J Winpenny RE 《Dalton transactions (Cambridge, England : 2003)》2004,(16):2550-2555
We report a carboxylate triangle consisting of three manganese(II) centres which is made from manganese(II) carbonate and pivalic acid. The magnetic exchange within the triangle is extremely weak, and antiferromagnetic. Several models have been used to fit the magnetic data, and the best fit uses two weak antiferromagnetic coupling constants of J(1)=-0.588 cm(-1) and J(2)=-0.855 cm(-1). Exchange interactions between the metal centres has been calculated using DFT adopting all the three possible Heisenberg models for a trinuclear system and the results are compared with experimental values. Spin density distribution is used to analyse the nature of the coupling between the metal centres. EPR spectroscopy has been used to explore the nature of the ground state. Recrystallisation of the trinuclear compound from MeCN gives a polymer, while oxidation in air leads to a known compound--an edge-sharing bitetrahedral (MnIII2MnII4) cage. 相似文献
13.
Benjamin M. Gray Andrew L. Hector William Levason Gillian Reid Michael Webster Wenjian Zhang Marek Jura 《Polyhedron》2010
The reaction of o-C6H4(AsMe2)2 with VCl4 in anhydrous CCl4 produces orange eight-coordinate [VCl4{o-C6H4(AsMe2)2}2], whilst in CH2Cl2 the product is the brown, six-coordinate [VCl4{o-C6H4(AsMe2)2}]. In dilute CH2Cl2 solution slow decomposition occurs to form the VIII complex [V2Cl6{o-C6H4(AsMe2)2}2]. Six-coordination is also found in [VCl4{MeC(CH2AsMe2)3}] and [VCl4{Et3As)2]. Hydrolysis of these complexes occurs readily to form vanadyl (VO2+) species, pure samples of which are obtained by reaction of [VOCl2(thf)2(H2O)] with the arsines to form green [VOCl2{o-C6H4(AsMe2)2}], [VOCl2{MeC(CH2AsMe2)3}(H2O)] and [VOCl2(Et3As)2]. Green [VOCl2(o-C6H4(PMe2)2}] is formed from [VOCl2(thf)2(H2O)] and the ligand. The [VOCl2{o-C6H4(PMe2)2}] decomposes in thf solution open to air to form the diphosphine dioxide complex [VO{o-C6H4(P(O)Me2)2}2(H2O)]Cl2, but in contrast, the products formed from similar treatment of [VCl4{o-C6H4(AsMe2)2}x] or [VOCl2{o-C6H4(AsMe2)2}] contain the novel arsenic(V) cation [o-C6H4(AsMe2Cl)(μ-O)(AsMe2)]+. X-ray crystal structures are reported for [V2Cl6{o-C6H4(AsMe2)2}2], [VO(H2O){o-C6H4(P(O)Me2)2}2]Cl2, [o-C6H4(AsMe2Cl)(μ-O)(AsMe2)]Cl·[VO(H2O)3Cl2] and powder neutron diffraction data for [VCl4{o-C6H4(AsMe2)2}2]. 相似文献
14.
锌(II)与2,2′ 联吡啶 1,1′ 二氧化物bypyO2形成的配合物主要有[Zn(bipyO2)3](ClO4)·2H2O、[Zn(bipyO2)3](PtCl4)·2H2O和[Co(bipyO2)2(NCS)2]等。我们在DMF溶剂中合成了锌(II)与bipyO2形成的三核配合物,测定了它的组成及IR谱气敏特性,发现对氨气有很高的敏感性和选择性。用它制作的传感器具有灵敏度高、选择性好、能耗低和常温下工作的特点,在涉氨化工生产的自动控制和氨气泄漏报警方面有一定的应用前景。1 实验部分bipyO2按文献[1]制备,经重结晶得白色晶体。C10H8N… 相似文献
15.
Paneque M Sirol S Trujillo M Carmona E Gutiérrez-Puebla E Mongue MA Ruiz C Malbosc F Serra-Le Berre C Kalck P Etienne M Daran JC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(18):3869-3879
Compounds of rhodium(I) and rhodium(III) that contain ancillary hydrotris(pyrazolyl)borate ligands (Tp') react with monodentate and bidentate tertiary phosphanes in a step-wise manner, with incorporation of P-donor atoms and concomitant replacement of the Tp' pyrazolyl rings. Accordingly, [Rh(kappa3-TpMe2)(C2H4)(PMe3)] (1b), converts initially into [Rh(kappa2-TpMe2)-(PMe3)2] (3), and then into [Rh(kappa1-TpMe2)-(PMe3)3] (2) upon interaction with PMe3 at room temperature, in a process which can be readily reversed under appropriate experimental conditions. Full disengagement of the Tp' ligand is feasible to give Tp' salts of rhodium(I) complex cations, for example, [Rh(CO)(dppp)2]-[TpMe2,4-Cl] (5; dppp = Ph2P(CH2)3PPh2), or [Rh(dppp)2][TpMe2,4-Cl] (6). Bis(hydride) derivatives of rhodium(III) exhibit similar substitution chemistry, for instance, the neutral complex [Rh(Tp)-(H)2(PMe3)] reacts at 20 degrees C with an excess of PMe3 to give [Rh(H)2-(PMe3)4][Tp] (9b). Single-crystal X-ray studies of 9b, conducted at 143 K, demonstrate the absence of bonding interactions between the [Rh(H)2(PMe3)4]+ and Tp ions, the closest Rh...N contact being at 4.627 A. 相似文献
16.
17.
The synthesis and structural characterization of the first example of a uranyl(VI) complex possessing unsupported unidentate thiolate ligands, UO2(S-2,6-Cl2C6H3)2L2 (2b, L=N,N-diisobutylisopropylamide), are reported. Isolation of 2b as a stable mononuclear complex is provided by the alkyl substituents of the organic amide ligands, which offer enhanced solubility, electron-releasing properties, and steric protection to help saturate the uranyl(VI) coordination sphere. 相似文献
18.
Treatment of a solid mixture of KBH4 with six equivalents of 3,5-diisopropylpyrazole (iPr2pzH) at 180 °C afforded KTpiPr2(iPr2PzH)3 in 53% yield. KBpiPr2 was synthesized in 56% yield by treatment of a 1:2 M ratio of KBH4 and iPr2PzH in refluxing dimethylacetamide. Treatment of MI2 (M = Ca, Sr, Ba) with two equivalents of KBp or KBpiPr2 in tetrahydrofuran afforded MBp2(THF)2 (M = Ca, 64%, M = Sr, 81%), BaBp2(THF)4 (32%), and M(BpiPr2)2(THF)2 (M = Ca, 63%; M = Sr, 61%, M = Ba, 48%) as colorless crystalline solids upon workup. These complexes were characterized by spectral and analytical techniques and by X-ray crystal structure determinations of all complexes except KBpiPr2. KTpiPr2(iPr2PzH)3 contains one κ3-N,N,N-TpiPr2 ligand and three κ1-iPr2pzH ligands, with overall distorted octahedral geometry about the K ion. The iPr2PzH nitrogen-hydrogen bonds are engaged in intramolecular hydrogen bonding to the 2-nitrogen atoms of the TpiPr2 ligand. The solid state structures of MBp2(THF)2, BaBp2(THF)4, and M(BpiPr2)2(THF)2 contain κ3-N,N,H Bp and BpiPr2 ligands, which form through metal-nitrogen bond formation to the 2-nitrogen atoms of the pyrazolyl fragments and metal-hydrogen bond formation to one boron-bound hydrogen atom per Bp ligand. SrBp2(THF)2has the shortest metal-hydrogen interactions among the series. A combination of preparative sublimations, solid state decomposition temperatures, and thermogravimetric analysis demonstrated that MBp2(THF)2, BaBp2(THF)4, and M(BpiPr2)2(THF)2 undergo solid state decomposition at moderate temperatures. 相似文献
19.
Biernat A Schwalbe M Wallace D Reglinski J Spicer MD 《Dalton transactions (Cambridge, England : 2003)》2007,(22):2242-2244
The synthesis and structure of two related sodium complexes are reported which demonstrate that sulfur can preferentially complex to sodium irrespective of the presence of more apposite donor species such as DMF. 相似文献
20.
Nicasio MC Paneque M Pérez PJ Pizzano A Poveda ML Rey L Sirol S Taboada S Trujillo M Monge A Ruiz C Carmona E 《Inorganic chemistry》2000,39(2):180-188
The bis(ethylene) Rh species TpMe2Rh(C2H4)2(1*) (TpMe2 = tris(3,5-dimethyl-1-pyrazol-1-yl)hydroborate) has been obtained from [RhCl(C2H4)2]2 and KTpMe2. Complex 1* easily decomposes in solution to give mainly the butadiene species TpMe2Rh(eta74-C4H6). In the solid state its thermal decomposition follows a different course and the allyl TpMe2RhH(syn-C3H4Me) is cleanly obtained as a mixture of exo and endo isomers. The complexes Tp'Rh(C2H4)2 (Tp' = Tp, TpMe2) afford the monosubstituted species Tp'Rh(C2H4)(PR3) upon reaction with PR3 but react differently with L = CO or CNR: the Tp compound gives dinuclear [TpRh]2(mu-L)3 complexes, while, in the case of 1*, TpMe2Rh(C2H4)(L) species are obtained. The ethylene ligand of complexes TpMe2Rh(C2H4)(PR3) is labile, and several peroxo compounds of composition TpMe2Rh(O2)(PR3) have been isolated by their reaction with O2. All the mononuclear Rh(I) complexes are formulated as 18e- trigonal bipyramidal species on the basis of IR and NMR spectroscopic studies. A series of dihydride complexes of Rh(III) of formulation Tp'RhH2(PR3) have been prepared by the hydrogenation of the corresponding ethylene derivatives. Complexes [TpRh]2(mu-CNCy)3, TpMe2Rh(C2H4)(PEt3), and TpMe2Rh(O2)(PEt3) have been further characterized by X-ray diffraction studies. 相似文献