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1.
E. E. Martsinko A. G. Pesaroglo L. Kh. Minacheva I. I. Seifullina V. S. Sergienko A. V. Churakov 《Russian Journal of Inorganic Chemistry》2011,56(1):26-31
A new heteronuclear germanium barium complex with D-tartaric acid [Ba(H2O)4][Ge2(μ-Tart)2(μ-OH)2]·5H2O (I) (H4Tart is tartaric acid) was synthesized. The identity of compound I and its com- position were determined by elemental analysis and X-ray diffraction. The thermal stability of the compound
was studied; the coordination centers of the ligand were found from IR spectroscopy. The structure of I was determined by X-ray crystallography. Crystals I are tetragonal: a = 8.5033(2) ?, c = 30.9393(11) ?, V = 2237.10(11) ?3, Z = 4, space group P41, R1 = 0.0301 based on 4215 reflections with I > 2σ(I). In crystals I, neutral [Ge2(μ-Tart)2] dimers are linked in pairs by double hydroxyl bridges to form {[Ge2(μ-Tart)2(μ-OH)2]2−}∞ polymeric chains. Hydrated Ba2+ cations and crystal water molecules are in between the anionic chains. Polymeric complex anions, hydrated barium cations,
and H2O molecules are bound by a system of hydrogen bonds to form a framework. 相似文献
2.
Yi Long Zhu Li-Na Ding Bin Cheng Peng Liao Dai-Zheng Zhai Yu-Ping Yan Shi-Ping Jiang Zong-Hui 《Transition Metal Chemistry》2004,29(2):200-204
Two novel complexes, [Cu(HL)2(H2O)]2(OH)2(ClO4)2·1.5H2O (1) and [Cu(HL)2]Cl2·4H2O (2), have been prepared by reacting copper salts with the 4-amino-3-ethyl-1,2,4-triazole-5-thione (HL) ligand in neutral solution and in HCl (6 mol L–1) medium, respectively. They were characterized by FT-IR and u.v.–vis. spectra, and the structures were determined by single crystal X-ray diffraction techniques. In both complexes, the triazole ligand chelated the metal ions through the amine and thione substituents on the five-membered ring. Complex (1) has a square-pyramidal copper(II) ion coordinated by two triazole ligands and one water molecule. Unlike (1), the Cu2+ ion in (2) displays its characteristic Jahn–Teller distortion with the distance of the Cl– anions to metal ion further away than that of the triazole ligands. The most intriguing structural features of the title complexes are that the HL ligands chelate copper(II) ions through the N(1) and S(1) atoms, in a cis mode in (1) and a trans mode in (2). In both cases, self-assembled crystals, by supramolecular contacts simultaneously, form two multi-dimensional frameworks. 相似文献
3.
Thermal reaction of [Ru2(CO)6(μ-PFu2)(μ-η1,η2-Fu)] (Fu=2-furyl) with (9-anthracenyl)diphenylphosphine (AnPPh2) produces a novel diruthenium complex [Ru2(CO)5(μ-PFu2)(μ-η1,η1,η2-C14H8PPh2)] (1) in good yield whereas the corresponding reaction between [(μ-H)4Ru4(CO)12] and AnPPh2 gives [HRu(CO)3(PPh2C14H8)][(μ-H)4Ru4(CO)11(AnPPh2)] (2). Both compounds 1 and 2 were fully characterized by spectroscopic methods and their X-ray crystal structures were determined. For 1, initial coordination of the PPh2 functionality at the Ru atom is accompanied by cyclometalation of the anthracenyl ring to form a Ru–C σ bond together with concomitant formation of a π bond to the adjacent Ru center and loss of the furyl ligand. The formation of 2 involves the cleavage of two Ru–Ru bonds, and the making of a Ru–P bond, followed by orthometalation of the anthracenyl ring. The optical absorption and emission spectra of 1 were recorded and the results were correlated to the DFT calculations.Dedicated to Professor F. Albert Cotton on the occasion of his 75th birthday. 相似文献
4.
Dawei Li Yafei Li David Felipe Tello Yepes Xiamei Zhang Prof. Dr. Yahong Li Prof. Dr. Jin-lei Yao 《化学:亚洲杂志》2021,16(17):2545-2551
A hexanuclear heterometallic cluster of composition [Dy2Co4(L)4(NO3)2(OH)4(C2H5OH)2] ⋅ 2 C2H5OH ( 1 ) was synthesized by employing a Schiff base 2-(((2-hydroxy-3-methoxybenzyl) imino)methyl)-4-methoxyphenol (H2L) as ligand and utilizing Dy(NO3)3 ⋅ 6H2O and Co(NO3)2 ⋅ 6H2O as metal ion sources. X-ray single-crystal diffraction analysis indicated that complex 1 contains a defect tetracubane core and possesses central symmetric structure, with two DyIII ions being in the central body position of the molecule and four CoII ions being arranged at the outer sites. Magnetic studies reveal that complex 1 behaves as single-molecule magnet (SMM) with energy barrier of 27.50 K. To investigate the individual contribution of DyIII and CoII ions to the SMM behavior, another two complexes of formulae [Dy2Zn4(L)4(NO3)2(OH)4] ⋅ 4CH3OH ( 2 ) and [Y2Co4(L)4(NO3)2(OH)4(C2H5OH)2] ⋅ 2 C2H5OH ( 3 ) were prepared. Complexes 1 and 3 are isomorphous. The coordination geometries of DyIII ions in 1 and 2 are different. The DyIII ions are eight-coordinated in 2 and nine-coordinated in 1 . Complex 2 exhibits SMM behavior with energy barrier of 69.67 K, but complex 3 does not display SMM property. These results reveal that the SMM behaviors of 1 and 2 are mainly originated from DyIII ions. It might be the higher symmetry of DyIII ions in 2 that results in the higher energy barrier. 相似文献
5.
Christine T. Wilcox Michael C. Jennings Roland K. Pomeroy 《Journal of Cluster Science》2004,15(2):107-117
The cluster Os7(CO)20(CNBu
t
) (1) has been prepared in 25% yield by the reaction of Os6(CO)18 with Me3NO and Os(CO)4(CNBu
t
) at –78°C. The crystal structure of 1 reveals the expected capped octahedral arrangement of metal atoms with the noncarbonyl ligand attached to the capping Os atom. The OsOs lengths in the two independent molecules in the unit cell are in the range 2.823(1)–2.922(1) Å, with the longer bonds associated with the Os3 triangle farthest from the capping Os atom. The 13C NMR spectrum of 1 in solution at room temperature has a 3:3:1 pattern that is consistent with rotation of the individual Os(CO)2(L) (L=CO or CNBu
t
) groups in the cluster. This in turn supports the idea that the capping Os(CO)2(CNBu
t
) unit binds to the central Os6 via a centrally directed MO plus two tangential molecular orbitals. 相似文献
6.
Reacting Re(CO)5Cl with the azopyridine ligand (1) (L) in boiling benzene afford the complex Re(CO)3Cl(L), (2) in excellent yield [L=2-(p-Cl-C6H4NN)C5H4N]. The chelation of the azopyridine ligand accompanied by displacement of the two carbon monoxide ligands furnish a five-membered chelate ring. Structure determination of complex (2) has revealed a distorted octahedral ReC3N2Cl coordination sphere. The Re–N(pyridine) and, Re–N(azo) distances are 2.158(3) and 2.153(6) Å respectively, and the N–N length [1.273(4) Å], implicate relatively weak Re-azo(π*) back–bonding. The Re(CO)3Cl(L) lattice consists of C–H...Cl hydrogen bonding and Cl...O non-bonded interactions constituting a supramolecular network. Extended Hückel calculations reveal that the LUMO of Re(CO)3Cl(L) is Ca. 57% azo in character. One-electron quasireversible electrochemical reduction of the complex occurs near −0.3 V versus Saturated Calomel electrode(s.c.e.) The redox orbital is believed to belong to the above noted LUMO. Electrogenerated Re(CO)3Cl(L•–) underwent spontaneous solvolytic chloride displacement in MeCN, resulting in the isolation of Re(CO)3(MeCN)(L•–). The latter complex in turn reacted with imidazole and triphenylphosphine, furnishing Re(CO)3(C3H4N2)(L•–) and Re(CO)3(PPh3)(L•–), respectively. The pattern of carbonyl stretching frequencies of these radical anion complexes is similar to that of Re(CO)3Cl(L) but with shifts to lower frequencies by 10–20 cm−1. All three radical anion systems are one-electron paramagnetic (1.7–1.8 μB). The unpaired electron is primarily localized on the azoheterocycle ligand in a predominantly azo-π* orbital, but a small metal contribution (185, 187Re, I=5/2) is also present. Thus Re(CO)3(MeCN)(L•–) and Re(CO)3(C3H4N2)(L•–) display six-line e.p.r. spectra (A ˜ 28 G). The line shapes and intensities are characteristic of the presence of g-strain. In the case of Re(CO)3(PPh3)(L•–) seven nearly equispaced lines are observed due to virtually equal coupling between the metal and 31P (I=&frac;) nuclei. The g-values of the radical species are slightly higher than the free-electron value of 2.0023. 相似文献
7.
Tkachev A. V. Savel'eva Z. A. Rybalova T. V. Gatilov Yu. V. Ikorskii V. N. Larionov S. V. 《Russian Journal of Coordination Chemistry》2001,27(12):871-877
Methods were developed for synthesizing the 3-Carene derivative (1R)-1-|(1R,2R,5R)-2-benzyl-3-imino-6,6-dimethylbicyclo[3.1.0]hex-2-yl}-ethanol (HL) and stable copper(II) complexes [Cu2(H2O)L2(CH3COO)2] · H2O (IV), [Cu2L2Cl2] (V), and [Cu2L2Br2] (VI). According to X-ray diffraction data, IVand Vhave molecular binuclear structures with a planar Cu2O2cycle. The CuOCu angles are equal to 102.2°, 102.8° (IV) and 103.2°, 103.8° (V). The L–terpene ligand acts as a tridentate cyclic bridge. A strong antiferromagnetic exchange interaction between the unpaired electrons of the copper(II) ions was detected in compounds IV–VIusing the static magnetic susceptibility method. The –2Jparameter for IV, V, and VIis equal to 660, 1000, and 1060 cm–1, respectively. 相似文献
8.
Mingos D. Michael P. Sherman Darren J. Williams Ian D. 《Transition Metal Chemistry》1987,12(6):493-496
Summary [RuCl(NO)2(dppbp)]BF4 (dppbp=(Ph2PCH2)2–) has been synthesised from [RuCl(NO)2(PPh3)2]BF4 and dppbp and characterised in the solid state by a single crystal x-ray determination. The [RuCl(NO)2(dppbp)]+ cation, has an approximately square-pyramidal co-ordination geometry with the dppbp ligand occupyingtrans-basal sites. The nitrosyl ligand in the apical site is partially bent [Ru–N–O=156.2(7)0] and the nitrosyl ligand in the basal side is essentially linear [Ru–N–O=172.5(6)0]. The1Hn.m.r. spectrum of [RuCl(NO)2(dppbp)]BF4 in solution has provided some insight into the dynamics of the complex in solution. 相似文献
9.
The reaction of ctc-[Ru(RaaiR′)2Cl2] (1) [RaaiR′ = 1-alkyl-2-(arylazo)imidazole, p-R-C6H4-N=N-C3H2NN(1)-R′, R = H (a), Me (b), Cl (c), R′ = Me (2), Et (3), Bz (4)] with (NH4)2MoS4 in aqueous MeOH afforded red-violet mixed ligand complexes of the type [(RaaiR′)2Ru(μ-S)2Mo(OH)2] (2–4). In complexes (2–4) the terminal Mo=S bonds of the MoS42− unit become hydroxylated and the molybdenum ion is reduced from the starting MoVI in MoS42− to MoIV in the final product (2–4). The solution electronic spectra exhibit a strong MLCT band at 550–570 nm in DCM. Cyclic voltammograms show a Ru(III)/Ru(II) couple at 1.10–1.4 V, irreversible Mo(IV)/Mo(V) oxidations in the 1.66–1.72 V range, along with four successive reversible ligand reductions in the range −0.45–0.67 V (one electron), −0.82–1.12 V (one electron), and −1.44–1.90 V (simultaneously two electrons). 相似文献
10.
In the presence ofEt
3N·PF5, F4P–(CH3N)2PF2NHNH+(CH3)2 (I) looses one molecule of HF to yield F3P(CH3N)2PF2NHN(CH3)2 (II). The reaction ofI withDABCO (1,4-diazabicyclo[2.2.2]octane) yieldsDABCO·2H++(CH3NPF4)
2
––
(III) and [CH3NPF2NHN(CH3)2]2 (IV). Even in the presence of CsF,II does not react with HF. 相似文献
11.
T. V. Mitkina D. Yu. Naumov O. A. Gerasko F. M. Dolgushin C. Vicent R Llusar M. N. Sokolov V. P. Fedin 《Russian Chemical Bulletin》2004,53(11):2519-2524
The inclusion compound of macrocyclic cavitand cucurbit[8]uril (CB[8]) with the nickel(II) complex containing the tetraazamacrocyclic ligand cyclam, {[Ni(cyclam)]@CB[8]}Cl2··16H2O (1), and the inclusion compounds of CB[8] with the copper(II) bis-ethylene-diamine complex, {trans-[Cu(en)2(H2O)2]@CB[8]}Cl2·{CB[8]}·42H2O (2a) and {trans-[Cu(en)2(H2O)2]@CB[8]}Cl2·17H2O (2b), were synthesized and characterized by X-ray diffraction analysis, IR and ESR spectroscopy, and electrospray mass spectrometry. Guest—host inclusion compounds can be directly synthesized starting from a metal complex and cucurbit[8]uril, as was exemplified by the preparation of compounds 2a and 2b.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2414–2419, November, 2004. 相似文献
12.
Alvaro Bernalte-García M. Angeles Díaz-Díez Fernando J. García-Barros Francisco J. Higes-Rolando Cristóbal Valenzuela-Calahorro 《Transition Metal Chemistry》1996,21(3):197-199
Summary The reaction of NiII ions with 2-(benzylamino)-2-deoxy-d-glycero-l-gluco. heptonic acid (BnGa:C14H21NO7) or 2-(benzylamino)-2-deoxy-d-glycero-d-talo heptonic acid (BnMa:C14H21NO7) in water yields complexes of formulae [Ni(BnGa)2(H2O)2] and [Ni(BnMa)2]·2H2O, respectively, which were characterized by elemental analysis, spectral techniques (u.v.-vis.-n.i.r. and i.r.), magnetic susceptibility measurements, thermal measurements (t.g. and d.s.c.) and X-ray powder diffraction. Both complexes are octahedral with two positions of the coordination sphere occupied by nitrogen atoms. Moreover, in [Ni(BnMa)2]·2H2O four oxygen atoms of bridging carboxylate groups are coordinated to the metal ion, while in [Ni(BnGa)2(H2O)2] only an oxygen atom of each carboxylate group is bound to NiII. In this case, the coordination is completed via two water molecules. 相似文献
13.
The bonding of the O-O group in the dicobalt cation 1a [(NH3)6Co2(μ-O2)(μ-OH)(μ-NH2)]3+ was studied by DFT methods (ADF program) and the bridging O2 ligand was characterized as superoxide(O2−). In this complex, three bridging ligands connect the two cobalt atoms, forcing a cis conformation of the Co-O-O-Co atoms. A comparison was made with [(NH3)10Co2(μ-O2)]5+, 2a, where a trans arrangement is observed. Superoxide binds more strongly to the dicobalt(III) fragment in 2a than in 1a, both as a result of weaker Pauli repulsion and stronger covalent interaction. It was found that in 1a the electronic structure with one unpaired electron, where cobalt is formally Co(III), d6, and O2 carries one negative charge gives rise to the most stable structure, compared to possibilities with three and five unpaired electrons. The hydrogen bonds in the crystal were analyzed and the interactions between one water molecule or one nitrate ion studied in more detail. 相似文献
14.
Reaction of α-amino acids (HL) with [Ru(PPh3)3Cl2] in the presence of a base afforded a family of complexes of type [Ru(PPh3)2(L)2]. These complexes are diamagnetic (low-spin d6, S=0) and show ligand-field transitions in the visible region. 1H and 31P NMR spectra of the complexes indicate the presence of C2 symmetry. Cyclic voltammetry on the [Ru(PPh3)2(L)2] complexes show a reversible ruthenium(II)–ruthenium(III) oxidation in the range 0.30–0.42 V vs. SCE. An irreversible ruthenium(III)–ruthenium(IV) oxidation is also displayed by two complexes near 1.5 V vs. SCE. 相似文献
15.
K. L. Tokarev M. A. Kiskin A. A. Sidorov G. G. Aleksandrov V. N. Ikorskii I. P. Suzdalev V. M. Novotortsev I. L. Eremenko 《Russian Chemical Bulletin》2008,57(6):1209-1214
The mononuclear complexes (η3-terpy)M(Piv)2·MeCN (M = Fe
ii
(3) and Co
ii
(4), and Piv is the pivalate anion) were synthesized by the reactions of polymeric iron(ii) and cobalt(ii) pivalates with 2,2′:6′,2″-terpyridine (terpy). The oxidation of compound 3 affords the pentanuclear heterospin iron(ii,iii) complex (η3-terpy)Fe5(μ4-O)(μ3-OH)(μ-OH)2(μ-Piv)7(η1-Piv)2 (5). All compounds were characterized by X-ray diffraction.
Dedicated to the 90th anniversary of the L. Ya. Karpov Institute of Physical Chemistry.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1186–1190, June, 2008. 相似文献
16.
以2,6-二甲基吡啶-3,5-二羧酸(H2L1)为主配体,1,10-菲咯啉(L2)为辅配体,分别与五水合硝酸镝、六水合硝酸铽及六水合硝酸铕通过水热法合成[Dy2(L1)3(L2)2]n(1)、{[Tb2(L1)3(L2)2]·5H2O}n(2)和{[Eu2(L1)3(L2)2]·5H2O}n(3)三种配合物。通过单晶X射线衍射、红外光谱、荧光光谱和热重分析对其结构进行了表征与性质研究。结果表明,配合物1~3均以稀土离子为金属节点连接配体L12-和L2,形成无限延伸的一维链状结构。 相似文献
17.
《无机化学与普通化学杂志》2018,644(8-9):443-448
A salen‐type Dy2 complex [Dy2(L)(MeOH)2(CH3COO)4] · 2(MeOH) was isolated and magnetically characterized, in which one hexadentate ligand H2L [H2L = N,N‐bis(2‐oxy‐3‐methoxybenzylidene)‐1,2‐phenylenediamine] chelated two DyIII ions, one is located on the apical position of the inner N2O2 site, leaving the outer O2O2 cavity for another DyIII ion. There are two distinct local coordination environments presented as square antiprism (D4d) for Dy1 and biaugmented trigonal prism (C2v) for Dy2. Magnetic measurements reveal that the ferromagnetic interaction between two DyIII ions occurred within low temperature range and accompanied with significant slow magnetic relaxation behavior with energy barriers to the reversal of magnetization Ueff/KB = 40 K under zero dc field. 相似文献
18.
Equilibria of Mo(VI) in acid aqueous solutions with excess of 2,3-dihydroxynaphthalene (DHN)c
DHN
/c
Mo = 2.3–107 (I = 0.6 mol 1–1 (NaClO4), 0.6% v/v ethanol) were studied spectrophotometrically. Formation constants of MoO2R
2
2–
(logK
012 = 5.89±0.01) and presumed MoO2(OH)(OH2)R– (logK
111 = 7.79±0.01) chelates were evaluated using SQUAD-G program. 相似文献
19.
O bin Shawkataly K. Ramalingam H.K. Fun A. Abdul Rahman I.A. Razak 《Journal of Cluster Science》2004,15(3):387-394
Syntheses and single crystal X-ray structures of an open triruthenium acyl carbonyl cluster [(C6H5)2SbRu3(COC6H5)(CO)10] (1) and a simple triruthenium Ru3(CO)9[(C6H5)2PCH2P(C6H5)2]Sb(C6H5)3
(2) are reported. Formation of compound (1) at room temperature from [Ru3(CO)12] and [Sb(C6H5)3] is unique, a similar reaction with Ru3(CO)10[(C6H5)2PCH2P(C6H5)2] under identical conditions results in compound (2), with Sb(C6H5)3 occupying an equatorial site. IR, 1H, 13C NMR spectra of the compounds are reported. The X-ray crystal structure of (1) consist of 2 crystallography distinct molecules and shows Ru–Sb distances in the range: 2.6361(6)–2.6273(7) Å and Ru–Ru distances in the range: 2.8236(7)–2.9855(7) Å. Ru–O distances in the bridging carbonyl are: 2.137(4), 2.158(4) Å. The Sb–Ru–Ru angles in the two molecules of the asymmetric unit are in the range of 73.78(2)–77.52° indicating the puckered nature. Compound (2) has bond parameters comparable to those of Ru3(CO)10[(C6H5)2PCH2P(C6H5)2]. The present study shows for the first time that the cleaving of Sb–C bond at room temperature is possible under non-ionic conditions, though there have been many instances of P–C and As–C bond cleavages reported previously. 相似文献
20.
The paper presents a combined experimental and computational study of Re(III) and Re(V) complexes containing di-2-pyridylketone and its gem-diol form – [ReCl3(dpk-N,O)(PPh3)] (1), [ReCl3(dpk-N,N′)(OPPh3)] (2) and [ReOBr3(dpk-OH)]·2(dpkH+Br−) (3). All the complexes have been characterized spectroscopically and structurally (by single-crystal X-ray diffraction). The complex 2 has been additionally studied by magnetic measurement. The magnetic behavior of 2 is characteristic of mononuclear octahedral Re(III) complex with d4 low-spin (3T1g ground state) and arise because of the large spin–orbit coupling (ζ = 2500 cm−1), which gives diamagnetic ground state. DFT and time-dependent (TD)DFT calculations have been carried out for [ReCl3(dpk-N,N′)(OPPh3)] and [ReOBr3(dpk-OH), and their UV–vis spectra have been discussed on this basis. 相似文献