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1.
The new acrylamide iron(II)/iron(III) complex [Fe(O-OC(NH2)CHCH2)6][Fe2OCl6] (1) was obtained by the reaction of a mixture of anhydrous FeCl2 and anhydrous FeCl3 with acrylamide (molar ratio 1:2:6) in 98% pure commercial nitromethane under nitrogen atmosphere. According to an X-ray structural analysis, the acrylamide ligands in the cation are coordinated via the amide-oxygen atoms. The formation of the (μ-oxo)bis[trichloroferrate(III)]2− anion presumably resulted from partial hydrolysis of FeCl3 or [FeCl4] by small amounts of water in the nitromethane and/or by the nitromethane itself.  相似文献   

2.
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   

3.
New linear and tripodal tetradentate ligands, LH2, are reported and their syntheses are described. The new linear ligands L = HSCH2CH2SCH2CH2NRCH2CR2SH, R = H, CH3) and the new tripodal ligands N(CH2CH2SH)2CH2Z, Z = CH2NH2, CH2N(CH3)2, CH2N(C2H5)2, CH2SCH3 and CO2- were synthesized. The known linear ligands HSCH2CH2NCH3(CH2)nNCH3CH2CH2SH (n = 2, 3) and HSCR2CH2NHCH2CH2NHCH2CR2SH (R = H, CH3) were also utilized. These ligands react with MoO2(acac)2 in CH3OH to yield MoO2L complexes in high yield. Infra-red and 1H nmr spectra provide evidence to supplement X-ray crystallographic results reported elsewhere for selected numbers of the series. Octahedral structures with cis MoO22+ groupings are assigned. Solution 1H nmr studies are consistent with a trans placement of the two thiolate donors in agreement with the X-ray studies.  相似文献   

4.
A 1:1 complex of mercuric chloride with D-peniccillamine has been isolated and characterised as 2[(μ3-Cl){HgSC(CH3)2CH(NH3)COO}3]·3(μ2-Cl)·2(H3O)·(H2O·Cl)3. The compound crystallises in cubic space group P4132, with a = 18.679(5) Å and Z = 4. The structure, refined to RF = 0.086 for 443 observed Mo-Kα diffractometer data, features a triply bridging chloride ion linking three equivalent [HgSC(CH3)2CH(NH3)COO]+ units [Hg-Cl = 2.37(1) Å, Hg-Cl-Hg′ = 98.5(9)°]. The carboxylate groups of a pair of adjacent penicillamine ligands are strongly linked via a symmetrical O?H?O hydrogen bond of length 2.24(8) Å, and neighboring pyramidal trinuclear [μ3-Cl){HgSC(CH3)2CH(NH3)-COO}3]2+ moieties are further connected by symmetrical chloride bridges [Hg-Cl = 3.06(2) Å; HgClHg′' = 79.6(7)°] to form a three-dimensional network. The voids in the lattice are filled by hydronium ions and novel planar cyclic hydrogen-bonded (H2O·Cl?)3 rings of edge O-H?Cl = 2.46(4) Å.  相似文献   

5.
Uranyl(VI) and thorium(IV) complexes of the type UO2(NO3)2(L1)2, UO2(NO3)2(L2)2, UO2(CH3COO)2L1, UO2(CH3COO)2L2, Th(NO3)4(L1)2 and Th(NO3)4(L2)2 (L1 = (2-nitro)phenyl-bis-phenyl phosphine oxide, L2 = triferrocenylphosphine oxide) are reported, together with their physico-chemical properties.The crystal structure of UO2(NO3)2(L1)2 is also reported. The crystals are monoclinic, space group P21/n with a = 17.78(1), b = 13.88(1), c = 17.37(1) Å, β = 114.8(1)° for Z = 4. The uranium atom is 8-coordinated, the uranyl(VI) group being equatorially surrounded by an irregular hexagon of six oxygen atoms from two trans neutral ligands and two nitrato groups.  相似文献   

6.
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   

7.
Carbamoyl methyl pyrazole compound of palladium(II) chloride of the type [PdCl2L2] (where L =  C5H7N2CH2CON(C4H9)2, C5H7N2CH2CON(iC4H9)2, C3H3N2CH2CON(C4H9)2, or C3H3N2CH2CON(iC4H9)2) has been synthesized and characterized by IR and 1H NMR spectroscopy. The structure of the compound [PdCl2{C3H3N2CH2CONiBu2}2] has been determined by single crystal X-ray diffraction and shows that the ligands are bonded through the soft pyrazolyl nitrogen atom to the palladium(II) chloride in a trans disposition.  相似文献   

8.
Complexes of the type [Pt(amine)4]I2 were synthesized and characterized mainly by multinuclear (195Pt, 1H and 13C) magnetic resonance spectroscopy. The compounds were prepared with different primary amines, but not with bulky amines, due to steric hindrance. In 195Pt NMR, the signals were observed between −2715 and −2769 ppm in D2O. The coupling constant 3J(195Pt-1H) for the MeNH2 complex is 42 Hz. In 13C NMR, the average values of the coupling constants 2J(195Pt-13C) and 3J(195Pt-13C) are 18 and 30 Hz, respectively. The crystal structure of [Pt(EtNH2)4]I2 was determined by X-ray diffraction methods. The Pt atom is located on an inversion center. The structure is stabilized by H-bonding between the amines and the iodide ions. The compound with n-BuNH2 was found by crystallographic methods to be [Pt(n-BuNH2)4]2I3(n-BuNHCOO). The crystal contains two independent [Pt(CH3NH2)4]2+ cations, three iodide ions and a carbamate ion formed from the reaction of butylamine with CO2 from the air. When the compound [Pt(CH3NH2)4]I2 was dissolved in acetone, crystals identified as trans-[Pt(CH3NH2)2(H3CNC(CH3)2)2]I2 were isolated and characterized by crystallographic methods. Two trans bonded MeNH2 ligands had reacted with acetone to produce the two N-bonded Schiff base Pt(II) compound.  相似文献   

9.
Takayuki Nagasawa  Toshi Nagata 《BBA》2007,1767(6):666-670
The synthesis and electrochemistry of half-sandwich type of Co(III) complexes [(C5Me5)Co(bidentate)(CH3CN)](BF4)2 {bidentate = dppe (1,2-bis(diphenylphosphino)ethane), dppp (1,3-bis(diphenylphosphino)propane), bpy (2,2′-bipyridine), en (ethylenediamine)) are reported. Cyclic voltammograms of [(C5Me5)Co(bidentate)(CH3CN)](BF4)2 in CH3CN s showed two redox couples assignable to Co(II)/Co(III) and Co(I)/Co(II). The Co(I) complex having C5Me5 and dppe was also prepared. Two redox couples of this Co(I) complex, (C5Me5)Co(dppe), in CH3CN coincided with those of [(C5Me5)Co(dppe)(CH3CN)](BF4)2 in spite of the structural change around the metal center.  相似文献   

10.
The 1,3-oxazine complexes cis- and trans-[PtCl2{ C(R)OCH2CH2C}H22] (cis: R=CH3 (1a), CH2CH3 (2a), (CH3)3C (3a), C6H5 (4a); trans:R =CH3 (1b), C6H5 (4b)) were obtained in 51-71% yield by reaction in THF at 0 °C of the corresponding nitrile complexes cis- and trans-[PtCl2(NCR)2] with 2 equiv. of OCH2CH2CH2Cl, generated by deprotonation of 3-chloro-1-propanol with n-BuLi. The cationic nitrile complexes trans-[Pt(CF3)(NCR)(PPh3)2]BF4 (R=CH3, C6H5) react with 1 equiv, of OCH2CH2CH2Cl to give a mixture of products, including the corresponding oxazine derivatives trans-[Pt(CF3){ CH2}(PPh3)2]BF4 (5 and 6), the chloro complex trans- [Pt(CF3)Cl(PPh3)2] and free oxazine H2. For short reaction times (c. 5–15 min) the oxazine complexes 5 and 6 could be isolated in modest yield (37–49%) from the reaction mixtures and they could be separated from the corresponding chloro complex (yield 40%) by taking advantage of the higher solubility of the latter derivative in benzene. For longer reaction times (> 2 h), trans-[Pt(CF3)Cl(PPh3)2] was the only isolated product. Complex 6 was crystallographically characterized and it was found to contain also crystals of trans- [PtCl{ H2}(PPh3)2]BF4, which prevented a more detailed analysis of the bond lengths and angles within the metal coordination sphere. The 1,3-oxazine ring, which shows an overall planar arrangement, is characterized by high thermal values of the carbon atoms of the methylene groups indicative of disordering in this part of the molecule in agreement with fast dynamic ring processes suggested on the basis of 1H NMR spectra. It crystallizes in the trigonal space group P , with a=22.590(4), b=15.970(3) Å, γ=120°, V=7058(1) Å3 and Z=6. The structure was refined to R=0.059 for 3903 unique observed (I3σ(I)) reflections. A mechanism is proposed for the conversion of nitrile ligands to oxazines in Pt(II) complexes.  相似文献   

11.
Several niobium and tantalum compounds were prepared that contain either the diamidoamine ligand, [(3,4,5-F3C6H2NCH2CH2)2NMe]2− ([F3N2NMe]2−), or the triamidoamine ligand, [(3,5-Cl2C6H3NCH2CH2)3N]3− ([Cl2N2NMe]3−). The former include [F3N2NMe]TaCl3, [F3N2NMe]NbCl3, [F3N2NMe]TaMe3, [F3N2NMe]NbMe3, [(F3N2NMe)TaMe2][MeB(C6F5)3], [F3N2NMe]Ta(CHSiMe3)(CH2SiMe3), [F3N2NMe]Ta(CH2-t-Bu)Cl2, [F3N2NMe]Ta(CH-t-Bu)(CH3), and [F3N2NMe]Ta(η2-C2H4)(CH2CH3). The latter include [Cl2N2NMe]TaCl2, [Cl2N2NMe]TaMe2, [Cl2N2NMe]Ta(η2-C2H4), and [Cl2N2NMe]Ta(η2-C2H2).X-ray diffraction studies were carried out on [F3N2NMe]Ta(CHSiMe3)(CH2SiMe3), [F3N2NMe]Ta(η2-C2H4)(CH2CH3), and [Cl2N2NMe]TaMe2..  相似文献   

12.
The coordination capability of the octaaza 24-membered (L1) and the tetraoxotetraaza 28-membered (L2) macrocycle ligands - with different sizes, nature and number of the donor atoms - has been investigated with nitrate and perchlorate Cd(II) salts. The complexes were prepared in 1:1 and 2:1 Cd:L molar ratio. The characterization by elemental analysis, IR, LSI mass spectrometry, conductivity measurements and 1H NMR spectroscopy, together with the crystal structure of the complexes [CdL1](NO3)2 · 0.5H2O, [CdL1](ClO4)2 and [CdL2(CH3CN)2](ClO4)2 · CH3CN · H2O confirms the formation of mononuclear complexes in all cases. The [CdL1](NO3)2 · 0.5H2O and [CdL1](ClO4)2 present a mononuclear endomacrocyclic structure with the metal ion coordinated by the eight donor nitrogen atoms from the macrocyclic backbone in a square antiprism geometry. The complex [CdL2(CH3CN)2](ClO4)2 · CH3CN · H2O is also mononuclear, but the cadmium ion is in an octahedral environment coordinated by four amine nitrogen atoms from the macrocyclic framework and two nitrogen atoms from two acetonitrile molecules. The ether oxygen atoms from the ligand are not coordinated.  相似文献   

13.
The reaction of [HRe3(CO)12]2− with an excess of Ph3PAuCl in CH2Cl2 yields [(Ph3PAu)4Re(CO)4]+ as the main product, which crystallizes as [(Ph3PAu)4Re(CO)4]PF6 · CH2Cl2 (1 · CH2Cl2) after the addition of KPF6.The crystal structure determination reveals a trigonal bipyramidal Au4Re cluster with the Re atom in equatorial position.If [(Ph3PAu)4Re(CO)4]+ is reacted with PPh4Cl, a cation [Ph3PAu]+ is eliminated as Ph3PAuCl, and the neutral cluster [(Ph3PAu)3Re(CO)4] (2) is formed.It combines with excess [(Ph3PAu)4Re(CO)4]+ to afford the cluster cation, [(Ph3PAu)6AuRe2(CO)8]+. It crystallizes from CH2Cl2 as[(Ph3PAu)6AuRe2(CO)8]PF6 · 4CH2Cl2 (3 · 4CH2Cl2). In [(Ph3PAu)3Re(CO)4] the metal atoms are arranged in form of a lozenge while in [(Ph3PAu)6AuRe2(CO)8]+ two Au4Re trigonal bipyramids are connected by a common axial Au atom.The treatment of [(Ph3PAu)4Re(CO)4]+ with KOH and Ph3PAuCl in methanol yields the cluster cation [(Ph3PAu)6Re(CO)3]+, which crystallizes with from CH2Cl2 as [(Ph3PAu)6Re(CO)3]PF6 · CH2Cl2 (4 · CH2Cl2). The metal atoms in this cluster form a pentagonal bipyramid with the Re atom in the axial position.  相似文献   

14.
Infrared, far-infrared and Raman spectra of Re2(O2CCH3)4X2 (X = Cl, Br) and Re2(O2CCD3)4Cl2 have been recorded. Assignments of the vibrational spectra of Os2(O2CCH3)4Cl2 and its deuterated derivative have been completed together with the Re complexes on the basis of normal-coordinate analysis. Force constant calculation was made for the acetate ion as well as for a four-atomic unit (with the CH3 and CD3 groups considered as point masses) using optimized masses of 16.7, 17.8, 20.5 and 21.6 for 12CH3, 13CH3, 12CD3 and 13CD3 groups, respectively. The force constants of the acetate ion have been adopted to the starting force field of the M2(O2CCH3)4X2 type complexes. The metal-halide (0.889, 0.997 and 1.286 N cm−1) and metal-metal stretching (3.32, 3.34 and 3.57 N cm−1) force constants were obtained for Re2(O2CCH3)4Cl2Re2(O2CCH3)4Br2 and Os2(O2CCH3)4Cl2 complexes, respectively. It was shown that the so-called diatomic approximation in most cases overestimates the M-M stretching force constants by 30-40%. Much better correlation has been obtained to fit these force constants, which produced values very close to those obtained by full normal-coordinate calculations. The Re-Re stretching force constants showed a reasonable correlation with the Re-Re bond distances for 18 rhenium complexes.  相似文献   

15.
The compounds W(CO)5P(C6H4-4-CH2CH2(CF2)7CF3)3 (1) and W(CO)5P(CH2CH2(CF2)5CF3)3 (2) were synthesized in order to probe the electronic and physical effects of ligation by perfluorocarbon substituted tertiary phosphine ligands in a W(CO)5L complex. The π-accepting ability of the fluorous phosphines was found to rank with non-fluorous comparators as P(CH2CH2(CF2)5CF3)3 > P(C6H4-4-CH2CH2(CF2)7CF3)3 > PPh3 > P(p-tolyl)3 > P(n-octyl)3. The X-ray crystal structure of W(CO)5P(C6H4-4-CH2CH2(CF2)7CF3)3 shows strong intermolecular association of fluorous components but confirms that the para fluorocarbon subtituents have an insignificant effect on the tungsten coordination environment. Partition coefficients (toluene/perfluoromethylcyclohexane) were measured for compounds 1 and 2.  相似文献   

16.
The structures of MoO2[NH2C(CH3)2CH2S]2 and MoO2[SC(CH3)2CH2NHCH2CH2NHCH2C(CH3)2S] have been determined using X-ray diffraction intensity data collected by counter techniques. MoO2[NH2C(CH3)2CH2S]2 crystallizes in space group Pbca with a = 11.234(3), b = 11.822(3) and c = 20.179(5) Å, V = 2680(2) Å3 and Z = 8. Its structure is derived from octahedral coordination with cis oxo groups [MoO = 1.705(3) and 1.705(3)], trans thiolate donors cis to the oxo groups [MoS = 2.416(1) and 2.402(1) and N donors trans to oxo [MoN = 2.325(3) and 2.385(4) Å]. MoO2[SC(CH3)2CH2NHCH2CH2NHCH2C(CH3)2S] crystallizes in the space group P21/c with a = 10.798(5), b = 6.911(2), c = 20.333(9) Å, β = 95.20°, V = 1511(2) Å3 and Z = 4. Its structure is very similar to that of MoO2[NH2C(CH3)2CH2S]2 with MoO = 1.714(2) and 1.710(2), MoS = 2.415(1) and 2.404(1) and MoN = 2.316(3) and 2.362(3). The small differences in the geometries of the two compounds are attributed to the constraints of the extra chelate ring in the complex with the tetradentate ligand. The structures in this paper stand in contrast to those reported for complexes of similar ligands wherein steric hindrance produces complexes with a skew trapezoidal bipyramidal structure.  相似文献   

17.
Phosphonium zwitterions of a known type were obtained in high yield via a 1:1 reaction of p-benzoquinone or methoxy-p-benzoquinone with the tertiary phosphines R3P [R = (CH2)3OH, Ph, Et, Me] and Ph2MeP, in acetone or benzene at room temperature. In all cases, attack of the P-atom occurs at a C-atom rather than at an O-atom. The products were characterized to various degrees by elemental analysis, 31P{1H}, 1H and 13C NMR spectroscopies, and mass spectrometry, and two of the zwitterions, the new [HO(CH2)3]3P+C6H2(O)(OH)(MeO) and the known Ph3P+C6H3(O)(OH), were structurally characterized by X-ray analysis. The PEt3 reaction also produces small amounts of the ‘dimeric’, μ-oxo co-product Et3P+C6H2(O)(OH)-O-C6H3(O)P+Et3 that is tentatively characterized by 1D- and 2D-NMR data. 2,5-Di-tert-butyl- and 2,3,5,6-tetramethyl-p-benzoquinone do not react with [HO(CH2)3]3P under the conditions noted above. Heating D2O solutions of the water-soluble zwitterions R3P+C6H3(O)(OH) [R = (CH2)3OH, Et] at 90 °C for 72 h leads to complete H/D exchange of the H-atom in the position ortho to the phosphonium center.  相似文献   

18.
The reaction of (diphoe)Pt(CH2CN)(OH) and trans-(PBz3)2Pt(Ph)(OH) with CO2 is reported as producing dimeric, bridged carbonato complexes of the type: P4Pt2(R)2(CO3). The crystal and molecular structure of (PBz3)4Pt2(Ph)2(μ-CO3)·(toluene) is also reported, showing η1, η1 bonding. The reaction is recognized to proceed in a stepwise fashion through bicarbonato intermediates.  相似文献   

19.
Hydrothermal reactions of lead(II) acetate and HO2C(CH2)3N(CH2PO3H2)2 at 170 and 140 °C, respectively, resulted in two different lead diphosphonates, namely, Pb2[NH(CH2PO3)2] · 2H2O (1), in which the butyric acid moiety of the HO2C(CH2)3N(CH2PO3H2)2 has been cleaved and a novel layered compound, Pb3[HO2C(CH2)3NH(CH2PO3)2]2 · 2H2O (2). Their crystal structures have been determined by single crystal X-ray diffraction. In compound 1, the interconnection of the lead(II) ions by bridging amino-diphosphonate ligands leads to the formation of a 3D network. Compound 2 features an unusual triple-layer structure with the non-coordinated butyric acid moieties as pendant groups between the layers.  相似文献   

20.
The reaction of α-MgCl2 with boiling ethyl acetate affords MgCI2(CH3COOC2H5)2· (CH3COOC2H5), which is obtained as crystals suitable for X-ray analysis only from the mother liquor. M=315.5, orthorhombic, space group P21221 (No. 18), a=25.077(3), b=8.616(1), c=7.345(1) Å, V=1587.0(3) Å3, Z=4, Dx=1.32 g cm−3,λ A(Mo Kα)=0.71069 Å, μ=4.17 cm−1, F(000)=664, T=298 K, observed reflections: 1667, R=0.059 and Rw=0.069. The structure is composed of polymeric chains of MgCl2(CH3COOC2H5)2 and the ethyl acetate molecules occupy a mutually trans position.  相似文献   

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