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1.
Four new dinuclear Mn(III) compounds have been synthesised: [{Mn(bpy)(H2O)}2(μ-4-ClC6H4COO)2(μ-O)}](ClO4)2 (1), [{Mn(EtOH)(phen)}2(μ-O)(μ-4-ClC6H4COO)2](ClO4)2 (2), [{Mn(bpy)(EtOH)}(μ-4-BrC6H4COO)2(μ-O){Mn(bpy)(ClO4)](ClO4) (3) and [{Mn(H2O)(phen)}2(μ-4-BrC6H4COO)2(μ-O)](ClO4)2 (4). The crystal structures of 2 and 3 are evidence for the tendency of the ethanol and the perchlorate to act as ligands. Due to the coordination of these groups, the environment of the manganese ions is elongated in the monodentate ligand direction, and this distortion is more important when this ligand is the perchlorate. The magnetic properties of the four compounds have been analysed: compounds 1, 3 and 4 show antiferromagnetic behaviour, with J = −6.33 cm−1 for 1, J = −6.76 cm−1 for 3 and J = −3.08 cm−1 for 4 (H = −JS1·S2), while compound 2 shows a very weak ferromagnetic coupling. For this compound, at low temperature the most important effect on the χMT data is the zero-field splitting of the ion, and the best fit was obtained with |DMn| = 2.38 cm−1 and |EMn| = 0.22 cm−1.  相似文献   

2.
The iron hydrido complex HFe(CO)2{P(OPh)3}{(PhO)2POC6H4} (1), was rapidly deprotonated by DBU or [BzMe3N][OH] in THF to afford the new carbonyl iron anion [Fe(CO)2{P(OPh)3}{(PhO)2POC6H4}] ([2]), containing an ortho-metallated triphenyl phosphite ligand. Complex [2] reacted with triorganostannyl and plumbyl salts and with halogens to give the octahedral FeII compounds Fe(CO)2{P(OPh)3}{(PhO)2POC6H4}(X) (X=SnPh3, 3; SnMe3, 4; PbPh3, 5; PbMe3, 6; Cl, 7; Br, 8; I, 9). The Group 14 complexes 3-6 were obtained in one isomeric form in which the PIII-donor atoms are mutually cis, the carbonyl ligands are cis and the P(OPh)3 and MR3 (M=Sn, Pb; R=Ph, Me) groups are trans as determined by solution-state IR, 31P and 13C NMR spectroscopic data. This geometry was confirmed for 3 by a single crystal X-ray diffraction study. The halide complexes, however, were obtained as a mixture of isomers. The major isomer (7, X=Cl; 8a, X=Br; 9a, X=I) has cis P atoms, trans CO groups and the halide located trans to the phosphorus atom of the ortho-metallated phosphite ligand. The structure of 9a was confirmed by an X-ray diffraction study. Two other isomers, designated 8b (X=Br) and 9b (X=I), with cis P atoms and cis CO groups were isolated from the reactions of [2] with Br2 and I2, respectively. The structure of the latter was established by X-ray crystallography and is related to 9a by exchange of the P(OPh)3 ligand and a carbonyl group such that the metal-bound C atom of the five-membered metallacycle is trans to CO. The stereo-geometry of 8b could not be unambiguously assigned from the spectroscopic data; however, two of the seven possible geometric isomers were suggested as plausible structures.  相似文献   

3.
Trityl borate salts [4-RPyCPh3][B(C6F5)4] (R = H 1, tBu 2, Et 3, NMe24) and [R3PCPh3][B(C6F5)4] (R = Me 5, nBu 6, Ph[1] 7, p-MeC6H48) are readily prepared via equimolar reaction of the appropriate pyridine or phosphine and trityl borate [CPh3][B(C6F5)4]. The analogous reactions of PiPr3 affords the product [(p-iPr3P-C6H4)Ph2CH][B(C6F5)4] (9) while the corresponding reactions of Cy3P and tBu3P gave the cyclohexadienyl derivatives [(p-R3PC6H5)CPh2][B(C6F5)4] (R = Cy 10, tBu 11). X-ray structures of 5 and 9 are reported.  相似文献   

4.
Reaction of Mo2(O2CCH3)2(DMepyF)2 (HDMepyF=N,N-di(6-methyl-2-pyridyl)formamidine) with HBF4 in CH2Cl2/CH3CN afforded the complex trans-[Mo2(H2DMepyF)2(CH3CN)4](BF4)6 (1), which crystallized in two forms, trans-[Mo2(H2DMepyF)2(CH3CN)4](ax-CH3CN)2(BF 4)6 · 2CH3CN (1a), and trans- [Mo2(H2DMepyF)2(CH3CN)4](ax-BF4) 2(BF4)4 · 2CH3CN (1b). The molecular structures of complexes (1) consist of two quadruply bonded molybdenum atoms, which are spanned by two trans-bridging formamidinate ligands and coordinated by four trans-CH3CN. Each H2DMepyF+ ligand adopts an s-cis,s-cis- conformation. The difference between 1a and 1b is that complex 1a contains two CH3CN molecules as axial ligands, while 1b contains two BF4 anions as axial ligands. Complex 1 is the first dimolybdenum complex containing a pair of trans bridging ligands and two pairs of trans-CH3CN ligands.  相似文献   

5.
Complexes of Ru(II) containing the pincer ligand [N(2-PPh2-4-Me-C6H3)2] (PNPPh) were prepared. The complex (PNPPhH)RuCl2 (1) was treated with 2 equiv AgOTf to produce the triflate complex (PNPPhH)Ru(OTf)2 (2). Complex 1 was also treated with an excess of NaBH4 to give a bimetallic complex [(PNPPh)RuH3]2 (3). A number of methods, including X-ray crystallography, NMR spectroscopy, and computational studies, were used to probe the structure of 3. Addition of Lewis bases to 3 resulted in octahedral complexes containing a hydride ligand trans to a dihydrogen ligand.  相似文献   

6.
The new aryl phosphinites PPh2OR (R = 2,4,6-Me3C6H2, 1; R = 2,6-Ph2C6H3, 2) have been prepared from chlorodiphenylphosphine and the corresponding phenols. In these ligands, the ortho-positions of the aromatic phosphite function are blocked by methyl and phenyl substituents, which allows coordination to metal centres without ortho-metallation. Thus, reaction with [PdCl2(cod)] leads to the complexes trans-[PdCl2(PPh2OR)2] (R = 2,4,6-Me3C6H2, 3; R = 2,6-Ph2C6H3, 4), while the reaction with [Rh2(CO)4Cl2] gives trans-[Rh(CO)Cl(PPh2OR)2] (R = 2,4,6-Me3C6H2, 5; R = 2,6-Ph2C6H3, 6). The single-crystal X-ray structure analyses of 3 and 5 confirm the trans-coordination of the new ligands in these square-planar complexes.  相似文献   

7.
Novel bipyridine-type linking ligands L1 ((4-py)-CHN-C10H6-NCH-(4-py)) and L2 ((3-py)-CHN-C10H6-NCH-(3-py)), a pair of isomers due to possessing different pairs of terminal pyridyl groups, were prepared by the Schiff-base condensation. In ligand L1, the N?N separation between the terminal pyridyl groups is 16.0 Å, with their nitrogen donor atoms at the para positions (4,4′). The corresponding N?N separation in ligand L2 is 14.2 Å, with the nitrogen donor atoms at the meta positions (3,3′). 1-D zigzag-chain coordination polymers [Zn(L1)(NO3)2] (1) and [Zn(L2)(NO3)2] (2) were prepared by reactions of Zn(NO3)2 · 6H2O with ligands L1 and L2, respectively, by solution diffusion. Polymer 3, [Cd(L1)1.5(NO3)2], prepared from Cd(NO3)2 · 4H2O and L1, exhibits a 1-D ladder structure, whose repeating ladder unit consists of four Cd metals and four L1 ligands to create a large 76-membered ring with dimensions of 20.8 × 20.8 Å. All products were structurally characterized by X-ray diffraction.  相似文献   

8.
The meta-diaminoaryl ferrocenes Fc-NCN-H (3) and Fc-CC-NCN-H (5) (Fc = (η5-C5H5)(η5-C5H4)Fe, NCN-H = C6H3(CH2NMe2)2-3,5) can be used as precursors in the preparation of heterobimetallic transition metal complexes of structural type Fc-NCN-MX (NCN = [C6H2(CH2NMe2)2-2,6]; MX = PdCl (7), PtCl (8), PtI (9)) and Fc-CC-NCN-MX (MX = PdCl (11), PdI (12), PtCl (13)), respectively. They are accessible by applying different synthesis procedures, including oxidative addition and metallation-transmetallation processes.Cyclovoltammetric studies show that the ferrocene moieties in 3, 5, 7-9 and 11-13 can reversibly be oxidised. The potential of the Fe(II)/Fe(III) redox couple decreases with increasing electron density at the NCN pincer unit. The use of 8 as a possible (electro)chemical sensor in the detection of SO2 is discussed as well.The solid-state structures of 8 and 13 are reported. The crystals of 8 contain two molecules of 8 in the asymmetric unit. The plane of the C6H2 moiety is with 27.2(3)° and 38.2(3)° tilted towards the C5H4 entity, while in 13 an angle of 45.9(3)° can be found. The d8-electron configured platinum atoms possess a somewhat distorted square-planar surrounding, setup by two Me2NCH2ortho-substituents, the NCN Cipso carbon atom and the chloride ligand.  相似文献   

9.
The preparation and characterization of yttrium(III) and europium(III) complexes of tripodal heptadentate Schiff-base ligand N[CH2CH2NCH(2-OH-3-MeC6H3)]3 (H3L1) have been studied. These complexes were prepared by the reaction of tris(2-aminoethyl)amine with 3-methylsalicylaldehyde in presence of M(CF3SO3)3 (M = Y, Eu) in methanol. The molecular structures of [YL1] (1) and [EuL1] (2) were determined by X-ray crystallography. The crystal structure analysis revealed that the Schiff-base behaves as a tri-deprotonated heptadentate ligand encapsulating the metal ion within the N4O3 cavity. Under the excitation of UV light, the solid state of these complexes exhibited blue and red emission, respectively. The optical properties of 1 and 2 in solution and in the solid state were examined.  相似文献   

10.
New copper(II) clofibriates (clof, {2-(4-chlorophenoxy)-2-methylpropionic or 2-(4-chlorophenoxy)isobutyric acid}) of composition Cu(clof)2L2 (where L=2-pyridylmethanol (2-pymeth) (1), N-methylnicotinamide (Menia) (4), N,N-diethylnicotinamide (Et2nia) (5), isonicotinamide (isonia) (7) or methyl-3-pyridylcarbamate (mpc) (8)), [Cu(clof)2(4-pymeth)2(H2O)] · 2H2O (4-pymeth=4-pyridylmethanol) (2 · 2H2O) and Cu(clof)2L (where L=4-pymeth (3) or Et2nia (6)) have been prepared and spectroscopically characterized. All the Cu(clof)2L2 compounds seem to possess distorted octahedral copper(II) stereochemistry with differing tetragonal distortions. An X-ray analysis of 1 was carried out and it featured a tetragonal-bipyramidal geometry around the copper(II) atom. X-ray analysis of 2 · 2H2O featured a square-pyramidal geometry around copper(II) atom. Both the Cu(clof)2L compounds seem to consist of a binuclear unit of tetracarboxylate type bridging. An X-ray analysis of 6 revealed typical binuclear paddle-wheel type structure, consisting of two copper(II) atoms in square-pyramidal geometry bridged by four carboxylate anions in the xy-plane. All complexes under study were characterized by EPR and electronic spectroscopy. The antimicrobial effects have been tested on various strains of bacteria, yeasts and filamentous fungi.  相似文献   

11.
The molecular structure of an o-phenylenediamine unit-containing oligophenylene (1), Ph-Ph′-Ph′(2,3-NH2)-Ph′-Ph (Ph = phenyl; Ph′ = p-phenylene; Ph′(2,3-NH2) = 2,3-diamino-p-phenylene), was determined by X-ray crystallography. 1 has a twisted structure, and forms an intermolecular C-H?π interaction network. The -NH2 group of 1 was air-oxidized to an imine, NH, group in the presence of [RuCl2(bpy)2] (bpy = 2,2′-bipyridyl) and gave a ruthenium(II)-benzoquinone diimine complex [Ru(2)(bpy)2](PF6)2 (2: Ph-Ph′-Ph′(2,3-imine)-Ph′-Ph). The molecular structure of [Ru(2)(bpy)2](PF6)2 was confirmed by X-ray crystallography. [Ru(2)(bpy)2](PF6)2 underwent two-step electrochemical reduction with E1/2 = −0.889 V and −1.531 V versus Fc+/Fc. The E1/2’s were located at higher potentials by 91 mV and 117 mV, respectively, than those of reported [Ru(bqdi)(bpy)2](PF6)2 (bqdi = benzoquinone diimine). Electrochemical oxidation of [Ru(2)(bpy)2](PF6)2 occurred at a lower potential by 180 mV than that of [Ru(bqdi)(bpy)2](PF6)2. Occurrence of the easier reduction and oxidation of [Ru(2)(bpy)2](PF6)2 than those of [Ru(bqdi)(bpy)2](PF6)2 is ascribed to the presence of a large π-conjugation system in 2.  相似文献   

12.
A series of bifunctional chelates of the type dipicolylamino-alkylcarboxylate (NC5H4CH2)2N(CH2)nCO2H (n = 1-4; HL1-HL4, respectively) has been prepared. Reactions of the ligands in aqueous methanol/N,N-dimethylformamide with the appropriate Cu(II) salts yielded the compounds [CuL1](NO3)·H2O (1·H2O), [CuL2(H2O)]BF4·H2O (2·H2O), [Cu(HL3)(SO4)]2 (3) and [CuL4(NO3)]·MeOH (4·MeOH). While compounds 1, 2 and 4 are one-dimensional, the detailed connectivities within the chains are quite distinct, depending on factors such as alkyl chain length and ligation of aqua ligands or anionic components. In contrast to 1, 2 and 4, the structure of 3 is molecular, a binuclear assembly of edge-sharing Cu(II) ‘4+2’ distorted octahedra. The Cd(II) species, [{CdL2}2(SO4)]·4H2O (5·4H2O), prepared from HL2 and CdSO4·nH2O in aqueous methanol/N,N-dimethylformamide, is two-dimensional, with a network constructed from binuclear units of seven coordinate Cd(II), , linked through bridging SO42− groups to produce an assembly of linked hexagonal rings [{CdL2}2(SO4)]6.  相似文献   

13.
Two new rhenium(IV) mononuclear compounds of formula NBu4[ReBr4(OCN)(DMF)] (1) and (NBu4)2[ReBr(OCN)2(NCO)3] (2) (NBu4 = tetrabutylammonium cation, OCN = O-bonded cyanate anion, NCO = N-bonded cyanate anion and DMF = N,N-dimethylformamide) have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. 1 crystallizes in the monoclinic system with the space group P21/n, whereas 2 crystallizes in the triclinic one with as space group. In both complexes the rhenium atom is six-coordinated, in 1 by four Br atoms in the equatorial plane, and two trans-oxygen atoms, one of a DMF molecule and another one from a cyanato group, while in 2 by one bromide anion and five cyanate ligands, two of which are O-bonded and three N-bonded, forming a somewhat distorted octahedral surrounding. Magnetic susceptibility measurements on polycrystalline samples of 1 and 2 in the temperature range 1.9-300 K are interpreted in terms of magnetically isolated spin quartets with large values of the zero-field splitting (|2D| is ca. 41.6 and 39.2 cm−1 for 1 and 2, respectively).  相似文献   

14.
The thermal reaction of Ru3(CO)12 with various carboxylic acids (benzoic, 4-hydroxyphenylacetic, ferrocenic, stearic, oleic, 4-(octadecyloxy)benzoic) in refluxing tetrahydrofuran, followed by addition of 5-(4-pyridyl)-10,15,20-triphenylporphyrin (L), gives the dinuclear complexes Ru2(CO)4(OOCR)2L2 (1: R = -C6H5, 2: R = -CH2-p-C6H4OH, 3: R = -C5H4FeC5H5, 4: R = -(CH2)16CH3, 5: R = -(CH2)7CHCH(CH2)7CH3, 6: R = -p-C6H4O(CH2)17CH3). Complexes 1-6 were characterised by IR, NMR, and ESI-MS as well as by elemental analysis. The UV-Vis spectra show the Soret band centred at 417 nm and the Q bands at 515, 550, 590 and 645 nm, respectively.  相似文献   

15.
Metal-sulfur complex fragments, to which small molecules like N2, N2H2, N2H4, NH3, or CO can bind, are desirable model compounds concerning enzymatic N2 fixation.This paper reports on the effects of the phosphane co-ligand on formation and reactivity of [Ru(L)(PR3)(`N2Me2S2')] [`N2Me2S2'2−=1,2-ethanediamine-N,N-dimethyl-N,N-bis(2-benzenethiolate)(2−)] complexes with nitrogenase relevant ligands, especially N2, N2H4, NH3, and CO.Treatment of [Ru(NCCH3)4Cl2] with Li2`N2Me2S2', excessive LiOMe, bulky PPh3 or PCy3, respectively, led to the formation of two series of [Ru(L)(PR3)(`N2Me2S2')] complexes [for R=Ph: 1b, 1c (L=NCCH3), 6b (L=N2H4), 7b (L=N2), 8b1-3 (L=CO), 9b (L=NH3); for R=Cy: 1a (L=NCCH3), 6a (L=N2H4), 7a (L=N2), 8a (L=CO), 9a (L=NH3)]. While the use of PPh3 (θ=145°) yielded cis,trans and cis,cis isomers of [Ru(NCCH3)(PPh3)(`N2Me2S2')] (1b, 1c), no isomer formation was observed with the bulkier phosphane PCy3 (θ=170°). Sterically less demanding phosphanes (θ=118-132°) afforded bisphosphane complexes [Ru(PR3)2(`N2Me2S2')] [2d (R=Me), 2e (R=Et), 2f (R=nPr), and 2g (R=nBu)], which were practically inert and could only be converted in two cases and under drastic reaction conditions into the CO complexes [Ru(CO)(PR3)(`N2Me2S2')] [4e (R=Et), 4f (R=nPr)]. The chelating bidentate phosphane dppe (bisdiphenylphosphanoethane) yielded exclusively the mononuclear complex [Ru(dppe)(`N2Me2S2')] (3).  相似文献   

16.
The synthesis and molecular structure of Me2LSn(1-Me-1,2-C2B10H10) (3), L is 2,6-(t-BuOCH2)2C6H3, the precursor for the synthesis of other Sn ← O intramolecularly coordinated organotin(IV) compounds containing 1-methyl-o-carborane (1-Me-1,2-C2B10H11) is reported. Compound 3 was characterized by the help of 1H, 11B, 13C, 119Sn NMR spectroscopy and X-ray diffraction technique. For the preparation of 3, a novel triorganotin(IV) compound Me2LSnCl (2) has been prepared since the reaction of sterically more demanding Ph2LSnCl (1) with 1-Me-1,2-C2B10H10Li did not occur.  相似文献   

17.
Addition of excess CF3CO2H (HTFA) to [Rh2Pt2(CO)7(PPh3)3], I, under nitrogen results in the formation of a salt (X2+ Y2−), which contains only the second example of a di-cationic carbonyl hydride tetra-nuclear cluster, [H2Rh2Pt2(CO)7(PPh3)3]2+, X2+, and a presently partially characterized polymetallic anion Y2−. The di-cation X2+ has been characterized by mass spectrometry and a variety of multinuclear NMR methods. Since there is no difference in the electron count for I and X2+, it is probable that both I and X2+ adopt similar butterfly metallic frameworks with a Rh-Rh hinge; in X2+, there are two bridging hydrides to the same wing-tip Pt but the phosphine site occupancies on the Rh2Pt2-framework in I and X2+ are different.  相似文献   

18.
It was found that the lanthanide diiodides LnI2 (1) (Ln = Nd, Sm, Eu, Dy, Tm, Yb) are dissolved in isopropylamine (IPA) without redox transformations. Stability of the formed solutions decreases in a row Eu ≈ Yb > Sm > Tm > Dy > Nd. Removing of a solvent in vacuum leaves complexes LnI2(IPA)x (2) (Nd, x = 5; Sm, Eu, Dy, Tm, Yb, x = 4) as crystalline colored solids. Stability of 2-Nd,Dy,Tm is higher than that of known THF or DME coordinated salts. Divalent state of metal in the products is confirmed by data of UV-Vis spectroscopy, magnetic measurements and their chemical behavior. Structure of 2-Eu and 2-Tm was established by X-ray diffraction analysis. Oxidation of 2-Nd,Dy in IPA affords amine-amides (PriNH)Ln(IPA)y (3) (Nd, y = 4; Dy, x = 3). n-Propylamine also dissolves the iodides 1-Sm,Eu,Dy,Tm,Yb but stability of the solutions is significantly lower. 1-Nd vigorously reacts with PrnNH2 even at −30 °C which hampers the formation of the solution.  相似文献   

19.
Two new zincophosphites [C6H14N2]0.5[Zn(H2PO3)2] 1 and [C4H12N2]0.5[(CH3)2NH2][Zn2(HPO3)3] 2 have been solvothermally synthesized in mixed solvents of N,N-dimethylformamide (DMF) and 1,4-dioxane (DOA), respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a neutral inorganic chain formed by ZnO4 and HPO2(OH) units. Interestingly, the left- and right-handed hydrogen-bonded helical chains are alternately formed via the hydrogen-bonds between two adjacent chains. Compound 2 exhibits a layer structure with 4- and 12-MRs formed by ZnO4 and HPO3 units, in which two kinds of organic amine molecules both act as countercations to compensate the overall negative electrostatic charge of the anionic network.  相似文献   

20.
The labile iridium(I) precursor trans-[IrCl(C8H14)(PiPr3)2] (2), prepared in situ from [IrCl(C8H14)2]2 (1) and PiPr3, reacted with equimolar amounts of 1,4-C6H4(CCSiMe3)2 (3) at 60 °C to give the mononuclear vinylidene complex trans-[IrCl(CC(SiMe3)C6H4CCSiMe3)(PiPr3)2] (4). From 2 and 3 in the molar ratio of 2:1, the dinuclear compound trans,trans-[(PiPr3)2ClIr(CC(SiMe3)C6H4C(SiMe3)C)IrCl(PiPr3)2] (5) was obtained. Reaction of 4 with [RhCl(PiPr3)2]2 (6) at room temperature afforded the heterodinuclear alkyne(vinylidene) complex trans,trans-[(PiPr3)2ClIr(CC(SiMe3)C6H4CCSiMe3)RhCl(PiPr3)2] (7), which on heating at 45 °C was converted to the bis(vinylidene) isomer trans,trans-[(PiPr3)2ClIr(CC(SiMe3)C6H4C(SiMe3)C)RhCl(PiPr3)2] (8).  相似文献   

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