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1.
Tanmay K. Jana Rabindranath Pradhan Subhajit Dinda Corine Simonnet Inhar Imaz Léopold Fournès Francis Sécheresse Ramgopal Bhattacharyya 《Inorganica chimica acta》2009,362(10):3583-3594
Iron (II) and iron (III) complexes, [FeII(DEDTC)2(dppe)] · CH2Cl2 (1), [FeII(ETXANT)2(dppe)] (2) (DEDTC = diethyldithiocarbamate, ETXANT = ethyl xanthate, dppe = 1,2-bis (diphenylphosphino) ethane), and [FeIII(DEDTC)2(dppe)] [FeIIICl4] (3) have been synthesized and characterized. Since 3 contains two magnetic centers, an anion metathesis reaction has been conducted to replace the tetrahedral FeCl4− by a non-magnetic BPh4− ion producing [FeIII(DEDTC)2(dppe)]BPh4 (4) for the sake of unequivocal understanding of the magnetic behavior of the cation of 3. With the similar end in view, the well-known FeCl4− ion, the counter anion of 3, is trapped as PPh4[FeIIICl4] (5) and its magnetic property from 298 to 2 K has been studied. Besides the spectroscopic (IR, UV-Vis, NMR, EPR, Mass and XPS) characterization of the appropriate compounds, especially 2, others viz. 1, 3 and 4 have been structurally characterized by X-ray crystallography. While FeII complexes, 1 and 2, are diamagnetic, the FeIII systems, namely the cations of 3, and 4 behave as low-spin (S = 1/2) paramagnetic species from 298 to 50 K. Below 50 K 3 shows gradual increase of χMT up to 2 K suggesting ferromagnetic behavior while 4 exhibits gradual decrease of magnetic moment from 60 to 2 K, indicating the occurrence of weak antiferromagnetic interaction. These conclusions are supported by the Mössbauer studies of 3 and 4. The Mössbauer pattern of 1 exhibits a doublet site for diamagnetic (2-400 K) FeII. The compounds 1, 2 and 4 encompass interesting cyclic voltammetric responses involving FeII, FeIII and FeIV. 相似文献
2.
Song LC Li CG Ge JH Yang ZY Wang HT Zhang J Hu QM 《Journal of inorganic biochemistry》2008,102(11):1973-1979
As the new H-cluster models, six diiron propanedithiolate (PDT) complexes with mono- and diphosphine ligands have been prepared and structurally characterized. The monophosphine model complex (μ-PDT)Fe2(CO)5[Ph2PNH(t-Bu)] (1) was prepared by reaction of parent complex (μ-PDT)Fe2(CO)6 (A) with 1 equiv of Ph2PNH(t-Bu) in refluxing xylene, whereas A reacted with 1 equiv of Me3NO · 2H2O in MeCN at room temperature followed by 1 equiv of Ph2PH to give the corresponding monophosphine model complex (μ-PDT)Fe2(CO)5(Ph2PH) (2). Further treatment of 2 with 1 equiv of n-BuLi in THF at −78 °C followed by 1 equiv of CpFe(CO)2I from −78 °C to room temperature afforded monophosphine model complex (μ-PDT)Fe2(CO)5[Ph2PFe(CO)2Cp] (3), whereas the diphosphine model complexes (μ-PDT)Fe2(CO)4(Ph2PC2H4PPh2) (4), (μ-PDT)Fe2(CO)4[(Ph2P)2N(n-Pr)] (5) and (μ-PDT)Fe2(CO)4[(Ph2P)2N(n-Bu)] (6) were obtained by reactions of A with ca.1 equiv of the corresponding diphosphines in refluxing xylene. All the new model complexes were characterized by elemental analysis, spectroscopy and particularly for 1 and 3-6 by X-ray crystallography. On the basis of electrochemical and spectroelectrochemical studies, model 5 was found to be a catalyst for HOAc proton reduction to H2, and for this electrocatalytic reaction an ECCE mechanism was proposed. 相似文献
3.
Xavier FR Peralta RA Bortoluzzi AJ Drago V Castellano EE Haase W Tomkowicz Z Neves A 《Journal of inorganic biochemistry》2011,105(12):1740-1752
In this work we report on the synthesis, crystal structure, and physicochemical characterization of the novel dinuclear [FeIIICdII(L)(μ-OAc)2]ClO4·0.5H2O (1) complex containing the unsymmetrical ligand H2L = 2-bis[{(2-pyridyl-methyl)-aminomethyl}-6-{(2-hydroxy-benzyl)-(2-pyridyl-methyl)}-aminomethyl]-4-methylphenol. Also, with this ligand, the tetranuclear [Fe2IIIHg2II(L)2(OH)2](ClO4)2·2CH3OH (2) and [FeIIIHgII(L)(μ-CO3)FeIIIHgII(L)](ClO4)2·H2O (3) complexes were synthesized and fully characterized. It is demonstrated that the precursor [FeIII2HgII2(L)2(OH)2](ClO4)2·2CH3OH (2) can be converted to (3) by the fixation of atmospheric CO2 since the crystal structure of the tetranuclear organometallic complex [FeIIIHgII(L)(μ-CO3)FeIIIHgII(L)](ClO4)2·H2O (3) with an unprecedented {FeIII(μ-Ophenoxo)2(μ-CO3)FeIII} core was obtained through X-ray crystallography. In the reaction 2 → 3 a nucleophilic attack of a FeIII-bound hydroxo group on the CO2 molecule is proposed. In addition, it is also demonstrated that complex (3) can regenerate complex (2) in aqueous/MeOH/NaOH solution. Magnetochemical studies reveal that the FeIII centers in 3 are antiferromagnetically coupled (J = − 7.2 cm− 1) and that the FeIII-OR-FeIII angle has no noticeable influence in the exchange coupling. Phosphatase-like activity studies in the hydrolysis of the model substrate bis(2,4-dinitrophenyl) phosphate (2,4-bdnpp) by 1 and 2 show Michaelis-Menten behavior with 1 being ~ 2.5 times more active than 2. In combination with kH/kD isotope effects, the kinetic studies suggest a mechanism in which a terminal FeIII-bound hydroxide is the hydrolysis-initiating nucleophilic catalyst for 1 and 2. Based on the crystal structures of 1 and 3, it is assumed that the relatively long FeIII…HgII distance could be responsible for the lower catalytic effectiveness of 2. 相似文献
4.
The reaction of [Fe3(CO)12] with diphenyl-2-pyridylphosphine (PPh2Py) in refluxing toluene for 1 h afforded three compounds, [Fe2(CO)6(μ-PPh2)(μ-κ2-C,N-C5H4N)] (1), [Fe(CO)4(κ1-P-PPh2Py)] (2), and [Fe(CO)3(κ1-P-PPh2Py)2] (3) in 23%, 10% and 3.5% yields after work-up, respectively. The PPh2Py ligand acts as a terminal P-donor ligand in 2 and 3, while in 1 it underwent a selective phosphorus-carbon(pyridyl) bond cleavage to afford phosphido- and pyridyl-bridged ligands. The complexes were characterized by elemental analysis, FAB-mass, FTIR, 1H and 31P-{1H}NMR spectroscopies. Compounds 1 and 2 were also characterized by X-ray single crystal. 相似文献
5.
A new mononuclear tetracyanometallic complex, (n-Bu4N)[(dbphen)Fe(CN)4] (1, dbphen = 5,6-dibromo-1,10-phenanthroline), has been prepared by reacting [(dbphen)FeII(py)2(SCN)2] and KCN in water and further oxidized with chlorine. With the use of 1 as building block, two trinuclear Fe2M complexes, [(dbphen)2Fe2(CN)8Cu(Me3tacn)]·3H2O (2), [(dbphen)2Fe2(CN)8Ni(dabhctd)]·2H2O (3) and a chain complex of squares [(dbphen)2Fe2(CN)8Co(MeOH)2]n (4), have been synthesized and structurally characterized. Magnetic studies show ferromagnetic coupling between FeIII and MII (M = Cu, 2; Ni, 3) ions bridged by cyanides in complexes 2 and 3, while complex 4 exhibits meta-magnetic behavior. 相似文献
6.
Complexes of the type (η4-BuC5H5)Fe(CO)2(P) (P = PPh2Py 3, PPhPy24, PPy35; Py = 2-pyridyl) were satisfactorily prepared. Upon treatment of 3 with M(CO)3(EtCN)3 (M = Mo, 6a; W, 6b), the pyridyl N-atom could be coordinated to the metal M, which then eliminates a CO ligand from the Fe-centre and induced an oxidative addition of the endo-C-H of (η4-BuC5H5). This results in a bridged hydrido heterodimetallic complex [(η5-BuC5H4)Fe(CO)(μ-P,N-PPh2Py)(μ-H)M(CO)4] (M = Mo, 7a, 81%; W, 7b, 76%). The reaction of 4 or 5 with 6a,b did not give the induced oxidative addition, although these complexes contain more than one pyridyl N-atom. The reaction of 4 with M(CO)4(EtCN)2 (M = Mo, 9a; W, 9b) produced heterodimetallic complexes [(η4-BuC5H5)Fe(CO)2(μ-P:N,N′-PPhPy2)M(CO)4] (M = Mo, 10a, 81%; W, 10b, 83%). Treatment of 5 with 6a,b gave [(η4-BuC5H5)Fe(CO)2(μ-P:N,N′,N″-PPy3)M(CO)3] (M = Mo, 12a, 96%; W, 12b, 78%). 相似文献
7.
Reaction of sodium picolinate with FeIII oxo-centered carboxylate triangles in MeCN in the presence of PPh4Cl yields (PPh4)[Fe4O2(O2CR)7(pic)2] (R = Ph (1), But (2)). Omitting the phosphonium cation produces [Fe8Na4O4(O2CPh)16(pic)4(H2O)4] (3), which contains two Fe4Na2 units bridged by two picolinate ligands. X-ray crystal structures of 1 and 3 are reported.Voltammetric profiles in MeCN show four one-electron reduction steps for complexes 1 and 2. Variable-temperature magnetic susceptibility measurements in polycrystalline samples of 1 and 3 reveal strong antiferromagnetic couplings leading to S = 0 ground states. 相似文献
8.
Larysa Penkova Vadim A. Pavlenko Franc Meyer Igor O. Fritsky 《Inorganica chimica acta》2010,363(12):3036-8436
The synthesis, crystal structure and magnetic properties of manganese(III) binuclear complexes [MnIII2(L-3Н)2(CH3ОH)4]·2CH3ОH (1) and [MnIII2(L-3Н)2(Py)4]·2Py (2) (L = 3-[(1E)-N-hydroxyethanimidoyl]-4-methyl-1H-pyrazole-5-carboxylic acid) are reported. The ligand contains two distinct donor compartments formed by the pyrazolate-N and the oxime or the carboxylic groups. The complexes were characterized by X-ray single crystal diffraction, revealing that both 1 and 2 consist of dinuclear units in which the two metal ions are linked by double pyrazolate bridges with a planar {Mn2N4} core. Cryomagnetic measurements show antiferromagnetic interaction with g = 1.99, J = −3.6 cm−1, Θ = −2.02 K for 1 and g = 2.00, J = −3.7 cm−1, Θ = 1.43 K for 2. 相似文献
9.
A series of osmium(VI) nitrido complexes containing pyridine-carboxylato ligands OsVI(N)(L)2X (L = pyridine-2carboxylate (1), 2-quinaldinate (2) and X = Cl (a), Br (1b and 2c) or CH3O (2b)) and [OsVI(N)(L)X3]− (L = pyridine-2,6-dicarboxylate (3) and X = Cl (a) or Br (b)) have been synthesised. Complexes 1 and 2 are electrophilic and react readily with various nucleophiles such as phosphine, sulfide and azide. Reaction of OsVI(N)(L)2X (1 and 2) with triphenylphosphine produces the osmium(IV) phosphiniminato complexes OsVI(NPPh3)(L)2X (4 and 5). The kinetics of nitrogen atom transfer from the complexes OsVI(N)(L)2Br (2c) (L = 2-quinaldinate) with triphenylphosphine have been studied in CH3CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law is obtained: −d[Os(VI)]/dt = k2[Os(VI)][PPh3]. OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) reacts also with [PPN](N3) to give an osmium(III) dichloro complex, trans-[PPN][OsIII(L)2Cl2] (6). Reaction of OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) with lithium sulfide produces an osmium(II) thionitrosyl complex OsII(NS)(L)2Cl (7). These complexes have been structurally characterised by X-ray crystallography. 相似文献
10.
Using a phosphorus based Mannich condensation reaction the new pyridylphosphines {5-Ph2PCH2N(H)}C5H3(2-Cl)N (1-Cl) and {2-Ph2PCH2N(H)}C5H3(5-Br)N (1-Br) have been synthesised in good yields (60% and 88%, respectively) from Ph2PCH2OH and the appropriate aminopyridine. The ligands 1-Cl and 1-Br display variable coordination modes depending on the choice of late transition-metal complex used. Hence P-monodentate coordination has been observed for the mononuclear complexes AuCl(1-Cl) (2), AuCl(1-Br) (3), RuCl2(p-cymene)(1-Cl) (4), RuCl2(p-cymene)(1-Br) (5), RhCl2(Cp∗)(1-Cl) (6), RhCl2(Cp∗)(1-Br) (7), IrCl2(Cp∗)(1-Cl) (8), IrCl2(Cp∗)(1′-Cl) (8′), IrCl2(Cp∗)(1-Br) (9), cis-/trans-PdCl2(1-Cl)2 (10), cis-/trans-PdCl2(1-Br)2 (11), cis-PtCl2(1-Cl)2 (12) and cis-PtCl2(1-Br)2 (13). Reaction of Pd(Me)Cl(cod) (cod = cycloocta-1,5-diene) with either 1 equiv. of 1-Br or the known pyridylphosphines 1′-Cl, 1-OH or 1-H gave the P/N-chelate complexes Pd(Me)Cl(1-Br-1-H) (14)-(17). All new compounds have been fully characterised by spectroscopic and analytical methods. Furthermore the structures of 4, 5, 10 and 16 · (CH3)2SO have been elucidated by single crystal X-ray crystallography. A crystal structure of the dinuclear metallocycle trans,trans-[PdCl2{μ-P/N-{Ph2PCH2N(H)}C5H4N}]2 · CHCl3, 18 · CHCl3, has also been determined. Here 1-H bridges, using both P and pyridyl N donors, two dichloropalladium centres affording a 12-membered ring with the PdCl2 units adopting a head-to-tail arrangement. 相似文献
11.
Silvia Melnic Charles Simmons Tatiana Chiriac Valeriu Rudic 《Inorganica chimica acta》2011,373(1):167-172
New trinuclear iron(III) furoates with the general formula [Fe3O(α-fur)6(R-OH)3]X, where α-fur C4H3OCOO, R = CH3 (1), C2H5 (2), n-C3H7 (3), n-C4H9 (4), X = NO3− (1-4); [Fe3O(α-Fur)6(DMF)(CH3OH)2]NO3 (5); [Fe3O(α-Fur)6(H2O)(CH3OH)2]Cl (6); [Fe2MO(α-Fur)6(L)(H2O)2], where L = THF (7-9), DMF (10-12), M = Mn2+ (7, 10), Co2+ (8, 11), Ni2+ (9, 12) and [Fe2MO(α-Fur)6(3Cl-Py)3], where M = Mn2+ (13), Co2+ (14), Ni2+ (15); have been prepared and investigated by Mössbauer and IR spectroscopy. The X-ray crystal structure for the 1·2CH3OH complex indicates that it crystallizes in the monoclinic crystal system (P21/n) and has a structure typical of μ3-O-bridged trinuclear iron(III) compounds. Coordination compounds 1, 4, 7, 8 can be used as regulators of the biochemical composition of cyanobacterium Spirulina platensis biomass. The supplementation of these compounds, in concentrations exceeding 5-10 mg/l, increases the content of iron, amino acids, peptides and carbohydrates in Spirulina. 相似文献
12.
Hitoshi Miyasaka Ayumi Saitoh Chihiro Kachi-Terajima Masahiro Yamashita 《Inorganica chimica acta》2005,358(12):3525-3535
A new class of mononuclear metal complexes with 1-methylimidazole-2-aldoximate (miao) has been synthesized and characterized: trans-NiII(Cl)2(Hmiao)2 (1), trans-NiII(miao)2(py)2 (2), NO-trans-NiII(miao)2(phen) (3), and NO-trans-FeII(miao)2(phen) (4). The crystal structures of 2, 3, and 4 have been determined by single-crystal X-ray crystallography. Compound 1 having the protonated miao ligand (i.e., Hmiao) is a precursor for synthesizing 2 and 3. Compound 2 is an octahedral NiII complex surrounded by two miao bidentate ligands and two monodentate ligands of pyridine in a trans-arrangement. Compound 3 is a cis-type octahedral NiII complex with two miao ligands and a bidentate ligand of 1,10-phenanthroline, in which the ligand arrangement around NiII center is found in an NO-trans form. Compound 4 is an isostructural FeII derivative of 3. Compounds 1, 2, and 3 exhibit paramagnetic nature with an S = 1 spin and a positive zero-field splitting, among which it for 3 is overlapped with intermolecular ferromagnetic interaction (zJ/kB = +0.16 K). Compound 4 is diamagnetic due to the existence of low-spin FeII ion. 相似文献
13.
The reaction of [PtMe3(MeOH)(bpy)][BF4] (1) with the thionucleobases 2-thiocytosine (SCy, 2) and 1-methyl-2-thiocytosine (1-MeSCy, 3) resulted in the formation of the complexes [PtMe3(bpy)(SCy-κS)][BF4] (4) and [PtMe3(bpy)(1-MeSCy-κS)] [BF4] (5), respectively. The complexes were characterized by 1H and 13C NMR spectroscopy as well as by single-crystal X-ray analyses of 4 · MeOH and 5. In 4 · MeOH two strong hydrogen bonds (N4-H?N3′: N4?N3′ 2.976(7) Å) between the thiocytosine ligands give rise to base pairing thus forming dinuclear cations [{PtMe3(bpy)(SCy-κS)}2]2+. In both complexes the platinum atom is octahedrally coordinated [PtC3N2S] by three methyl ligands, the 2,2′-bipyridine ligand and the κS coordinated nucleobase (configuration index: OC-6-33). The structural investigations gave evidence that the sulfur atoms of the nucleobase ligands in 4 · MeOH and 5 have to be regarded as sp3 and sp2 hybridized, respectively. Thus, the ligand in 4 · MeOH has to be considered as the deprotonated thiol-amino form of thiocytosine being reprotonated at N1. In complex 5 the 1-MeSCy is coordinated in its thione-amino form. DFT-calculations of the base-paired dinuclear cation in 4 as well as of 4 itself gave proof of the strength of the hydrogen bond (8.5 kcal/mol) and exhibited that cation-anion interactions influence the conformation of the complex. In vitro cytotoxicity studies of 4 and 5 using nine different human tumor cell lines revealed moderate cytotoxic activity. 相似文献
14.
Five new complexes, [Co3(HL1)2(Py)8]·4CH3OH (1), [Ni3(HL1)2(Py)4]2·2DMF (2), [Co3(H2L2)2(Py)8]·2NO3 (3), [Ni2(HL2)(Py)6] (4) and [Cu4(HL2)2(Py)4]·4DMF (5) (H4L1 = N-propionyl-4-hydroxysalicylhydrazide, H44-hopshz; H5L2 = N-(3-carboxy-cis-2-propenoyl)-4-hydroxysalicylhydrazide, H54-hocpshz) have been obtained from two N,N′-diacylhydrazide ligands and characterized by elemental analysis, FT-IR, X-ray diffraction and antimicrobial activities. These di-, tri-, and tetrameric complexes are connected into three-dimensional supramolecular architectures with interesting topologies through O-H?O, C-H?O and C-H?π interactions. 1-3 are linear trimeric complexes with the ligands triply-deprotonated. Topological analysis indicates that they exhibit 2D (4,4), 3D (6,8)-connected (3349526)(3441257647) and 8-connected (42563) net, respectively. 4 and 5 possess dimeric and tetrameric structures, which are extended into 7-connected (33413536) and 4-connected (4,4) net, respectively. 相似文献
15.
Prashant Kumar Mahendra Yadav Sanjay Kumar Singh Daya Shankar Pandey 《Inorganica chimica acta》2011,368(1):124-131
Synthesis and characterization of the ruthenium complexes [RuH(CO)Cl(κ1-P-PPh2Py)2(PPh3)] (1) and [Ru(CO)Cl2(κ1-P-PPh2Py)(κ2-P-N-PPh2Py)] (2) containing diphenyl-2-pyridylphosphine (PPh2Py) are described. Spectral and structural data suggested linkage of the PPh2Py in κ1-P bonding mode in 1 and both the κ1-P and κ2-P-N bonding modes in 2. The complex 1 reacted with N,N-donor bases viz., ethylenediamine (en), N,N′-dimethyl-(ethylenediamine) (dimen), 1,3-diaminopropane (diap), 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen) and di-2-pyridylaminomethylbenzene (dpa) to afford cationic complexes of formulation [RuH(CO)(κ1-P-PPh2Py)2(N-N)]+ (3-8) [N-N = en, 3; dimen, 4; diap, 5; bipy, 6; phen, 7; and dpa, 8], which have been isolated as their tetrafluoroborate salts. The complexes under investigation have been characterized by elemental analyses, spectroscopic and electrochemical studies. Molecular structures of 2, 3, 6, and 8 have been determined by single crystal X-ray diffraction analyses. Further, the complexes 1-8 act as effective precursor catalyst in transfer hydrogenation of acetophenone/ketones in basic 2-propanol. 相似文献
16.
Miao Du Cheng-Peng Li Yan-Ping You Xiu-Juan Jiang Hua Cai Qian Wang Jian-Hua Guo 《Inorganica chimica acta》2007,360(6):2169-2174
Assemblies of an angular dipyridyl ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo) with a series of metal perchlorate afford five new supramolecular complexes with the general formula of [M(4-bpo)2(H2O)4] · (4-bpo)2 · (anion) · (solvent), in which M = MnII for 1, FeII for 2, CoII for 3, ZnII for 4, and FeIII for 5. Although similar molecular structures and compositions are found for these mononuclear complexes, they display two types of supramolecular lattices. Complexes 1, 4 and 5 similarly crystallize in space group P2/n or P2/c. The complex cations, free 4-bpo and lattice water are linked to generate 2D layered frameworks with the aid of hydrogen bonding, and the counter anions are located within and between (also methanol in 5) these 2D arrays. However, complexes 2 and 3 are isostructural in space group . Two types of alternate 2D layers consisting of complex cations and free 4-bpo components, respectively, are observed with the anions and lattice water locating between them. These motifs are interlinked by complicated hydrogen-bonding to form a 3D intercalated network. Moreover, when Co(NO3)2 is used instead of Co(ClO4)2 in the assembly of 3, a 1D polymeric chain complex {[Co(4-bpo)(H2O)2(NO3)2](H2O)3}n (6) is generated. These results indicate that the choice of metal ion and anion exerts a significant influence on governing the target complexes. A comparison of the structural features for all metal perchlorate complexes with 4-bpo is also briefly discussed. 相似文献
17.
Jun-Jie Wang 《Inorganica chimica acta》2010,363(7):1377-1385
In our continuing efforts to explore the effects of substituent groups of ligands in the formation of supramolecular coordination structures, seven new CuII complexes formulated as [Cu2(L1)4(DMF)2] (1), {[Cu2(L1)4(Hmta)](H2O)0.75}∞ (2), [Cu2(L2)4(2,2′-bipy)2] (3), [Cu2(L3)4(H2O)2] (4), [Cu2(L3)4(Hmta)]∞ (5), [Cu2(L3)4(Dabco)]∞ (6) and [Cu2(L3)4(Pz)]∞ (7) with three monocarboxylate ligands bearing different substituent groups HL1-HL3 (HL1 = phenanthrene-9-carboxylic acid, HL2 = 2-phenylquinoline-4-carboxylic acid, HL3 = adamantane-1-carboxylic acid, Hmta = hexamethylenetetramine, 2,2′-bipy = 2,2′-bipyridine, Dabco = 1,4-diazabicyclo[2.2.2] octane and Pz = pyrazine), have been prepared and characterized by X-ray diffraction. In 1, 2 and 4-7, each CuII ion is octahedrally coordinated, and carboxylate acid acts as a syn-syn bridging bidentate ligand. While each CuII ion in 3 is penta-coordinated in a distorted square-pyramidal geometry. 1 and 4 both show a dinuclear paddle-wheel block, while 2, 5, 6 and 7 all exhibit an alternated 1D chain structure between dinuclear paddle-wheel units of the tetracarboxylate type Cu2-(RCO2)4 and the bridging auxiliary ligands Hmta, Dabco and Pz. Furthermore, 3 has a carboxylic unidentate and μ1,1-oxo bridging dinuclear structure with the chelating auxiliary ligand 2,2′-bipy. Moreover, complexes 1-6 were characterized by electron paramagnetic resonance (EPR) spectroscopy. 相似文献
18.
Pei-Chen Kuo 《Inorganica chimica acta》2005,358(13):3761-3767
Linked bis(ketimine) (1) can be prepared with the reaction of excess 2,4-pentanedione and 4,4′-methylene-bis(2,6-diisopropylaniline) in methanol in the presence of catalytic amount of formic acid. The dialuminum alkyl complexes containing the linked bis(ketiminate) dianionic ligands, [OC(Me)CHC(Me)N(2,6-iPr2C6H2-4)AlR2]2CH2 (2, R = Me; 3, R = Et), were prepared by a reaction of 2 equiv AlR3 with [OC(Me)CHC(Me)NH(2,6-iPr2C6H2-4)]2CH2 in methylene chloride. Reactions of 2 with 2 and 4 equiv of I2 gave corresponding aluminum iodo complexes 4 and 5, respectively. Treatment of 5 with 2 equiv of AgBF4, however, gave a diboron complex, [OC(Me)CHC(Me)N(2,6-iPr2C6H2-4)BF2]2CH2 (6), in 18% isolated yield. All new complexes have been characterized by 1H and 13C NMR spectroscopy and complexes 2, 3, and 6 are also confirmed by X-ray diffraction. 相似文献
19.
Paul Hamon Jean-François Meunier Loïc Toupet Michel Etienne Jean-René Hamon 《Inorganica chimica acta》2009,362(12):4389-11551
The white homoleptic high-spin iron(II) complexes Fe[TpMe2,4Cl]2 (1) was isolated in quantitative yield from reaction mixtures containing 1 equiv of FeCl2(THF)1.5 and 2 equiv of K[TpMe2,4Cl] (TpMe2,4Cl = hydrotris[(4-chloro-3,5-dimethyl-pyrazolyl)]borate). Its purple low-spin iron(III) counterparts 1[O3SCF3] and 1[PF6] were synthesized and isolated in 85% yields upon treatment of 1 with 1 equiv of silver triflate and silver hexafluorophosphate, respectively. The three paramagnetic compounds are air and thermally stable as solids and in solution; they were characterized by elemental analyses, IR, magnetic susceptibility measurements, 1H NMR, and Mössbauer spectroscopy. In addition, 1[PF6] was authenticated by a single-crystal X-ray diffraction. The two scorpionate ligands are κ3-N,N′,N′′ ligated to the central FeIII ion, forming an almost perfect FeN6 octahedron with an average Fe-N bond distance of 1.9551(18) Å. In addition, complex 1 which oxidizes reversibly at E1/2 = 0.483 V/SCE (ΔEp = 94 mV), remains high-spin (S = 2) when the temperature is lowered to 2 K. 相似文献
20.
Reactions of FeII, CoII, NiII, and ZnII salts with 6-quinolinecarboxylic acid (HL) under the hydrothermal conditions afford three monomeric complexes [M(L)2(H2O)4] (M = FeII for 1, CoII for 2, and NiII for 3) and a 1-D polymeric species {[Zn(L)2(H2O)] · H2O}n (4). The crystal structures of the ligand HL and these four complexes have been determined by using the X-ray single-crystal diffraction technique. The results suggest that complexes 1-3 are isostructural, displaying novel 3-D pillar-layered networks through multiple intermolecular hydrogen bonds, whereas in coordination polymer 4, the 1-D comb-like coordination chains are extended to generate a hydrogen-bonded layer, which is further reinforced via aromatic stacking interactions. Solid-state properties such as thermal stability and fluorescence emission of the polymeric ZnII complex 4 have also been investigated. 相似文献