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1.
Reactions of cobaloxime Na[(t-BuPy)Co(DH)2] with Ph3ECl (E = Si, Ge, Sn, and Pb) were investigated. Metal-metal bonded complexes (t-BuPy)Co(DH)2EPh3 were isolated for E = Sn and Pb. (t-BuPy)Co(DH)2SnPh3.(C2H5)2O, C39H52CoN5O5Sn, crystallized in the monoclinic space group P21/c (Z = 4) with unit cell dimensions a = 11.6443(6) A, b = 15.6085(8) A, c = 22.6354(12) A, beta = 96.634(1) degrees , and V = 4086.4(4) A3 at 295(2) K. The structure resembled those of six-coordinate alkyl cobaloxime complexes and had Co-NPy and Co-Sn distances of 2.056(2) and 2.5568(3) A, respectively. (t-BuPy)Co(DH)2PbPh3, C35H42CoN5O4Pb, crystallized in the monoclinic space group P21/n (Z = 4) with unit cell dimensions a = 15.0104(7) A, b = 15.7693(8) A, c = 16.6230(8) A, beta = 114.348(1) degrees , and V = 3584.8(3) A3 at 295(2) K. The complex was nearly isostructural with the Sn analogue and had Co-NPy and Co-Pb distances of 2.049(2) and 2.6191(4) A, respectively. Coupling of the ortho phenyl protons to the spin 1/2 isotopes of Sn and of Pb was a characteristic feature of the 1H NMR spectrum. Additional, longer range couplings were observed for the Pb complex and for both complexes in the 13C NMR. Metal-metal bonded complexes were not obtained for E = Si or Ge. The products isolated in the latter case were the hydride Ph3GeH and the cobalt(II) complex (t-BuPy)Co(DH)2,C17H27CoN5O4, which crystallized in the orthorhombic space group Pbcn (Z = 8). Unit cell dimensions were a = 17.9821(11) A, b = 9.7449(6) A, c = 22.7374(15) A, and V = 3984.4(4) A3 at 295(2) K. The five-coordinate complex had Co-NPy = 2.096(2) A and was dimeric in the lattice.  相似文献   

2.
A series of mono-, di- and trimeric oxo-centred triruthenium cluster compounds with ortho-metallated polypyridyl ligands were prepared by reaction of oxo-centred triruthenium precursor compound [Ru3O(OAc)6(py)2(CH3OH)]+ (1) with bis(2,2'-bipyridin-5-yl)butadiyne (bpyC[triple bond, length as m-dash]C-C[triple bond, length as m-dash]Cbpy), bis(2,2'-bipridin-5-yl)ethyne (bpyC[triple bond, length as m-dash]Cbpy), 2,2'-bipyrazine (bpz), pyrazino[2,3-f]quinoxaline (pyq), or 4,7-phenanthroline (4,7-phen). As revealed by redox wave splitting, electronic interactions are operating between two Ru3O redox centres in most of the triruthenium cluster dimers and trimers. The cluster-cluster interactions are highly sensitive to the variations in bonding modes of the polypyridyl ligands. Ortho-metallation of the bridging ligand induces an enhanced electronic interaction between two triruthenium centres.  相似文献   

3.
Neutral orthometalated platinum(II) complexes of the deprotonated 6-phenyl-2,2'-bipyridine ligand (bearing a trialkoxygallate, tolyl, ethynyltrialkoxygallate, or ethynyltolyl substituent) and a sigma-bonded Cl, ethynyltolyl, or ethynyltrialkoxygallate coligand have been prepared by a stepwise procedure based on copper-promoted cross-coupling reactions. The X-ray structure of the [2-(p-tolyl)ethynyl][4-{2-(p-tolyl)ethynyl}-6-phenyl-2,2'-bipyridyl)]platinum(II) complex revealed a coplanar arrangement of all residues bound to platinum, although the tolylethynyl groups exhibit position-dependent bending in the solid state. The complexes exhibit charge-transfer absorption in the visible region. All except two of the complexes also exhibit charge-transfer emission, typically from an excited state that has a submicrosecond lifetime at room temperature in deoxygenated dichloromethane solution. In accordance with the presence of a carbometalated polypyridine ligand, the emitting state is assumed to have a mixture of metal-to-ligand charge-transfer (MLCT) and intra-ligand charge-transfer (ILCT) character. However, spectral comparisons and electrochemical data suggest that the emissive state also exhibits interligand charge-transfer (LLCT) character when an electron-rich ethynylaryl group is bound to platinum. In keeping with altered orbital parentage in the latter systems, the emission occurs at longer wavelength. The excited-state lifetime is also shorter, evidently due to vibronic interactions. The decay is so efficient when an ethynyltrialkoxygallate group binds to platinum that there is no detectable emission in fluid solution, although the complexes do emit in a frozen glass. The excited states are subject to associative (exciplex) quenching by Lewis bases, but the admixture of ILCT and/or LLCT character diminishes efficiency, except for relatively strong bases like dimethyl sulfoxide and dimethylformamide.  相似文献   

4.
利用常规水溶液法制备了三种基于饱和Keggin结构阴离子的有机-无机复合杂多化合物[Pr(pydc)(H2O)6]2H[PMo12O40]·4H2O(1)、[Nd(pydc)(H2O)6]2H[PMo12O40]·4H2O(2)和[Tb(pydc)(H2O)6]2H[PMo12O40]·4H2O(3)(pydc=2,6...  相似文献   

5.
Four metal-organic coordination compounds containing ferrocenylthiocarboxylate components, [Cd22-SOCFc)212-SOCFc)2(4,4′-bpy)]n (1), [Cd(SOCFc)2(tmp)]n (tmp = 4,4′-trimethylene-dipyridine) (2) [Zn(SOCFc)2(2,2′-bpy)] (3), and {[Hg(SOCFc)2(phen)] · (0.5CH3OH)} (4) (Fc = (η5-C5H5)Fe(η5-C5H4)), have been prepared in search of good nonlinear optical (NLO) materials. Investigation of the NLO properties shows that Hg-containing compound 4 exhibits very strong third-order NLO absorptive and refractive effects. The NLO absorptive coefficient α2 value (2.11 × 10−10 m W−1) is larger than those of all the reported ferrocenylcarboxylate-containing coordination compounds and comparable to the well-performing Hg-containing complexes. Additionally, we further analyzed their NLO behaviors through studying electrochemical properties of the four compounds.  相似文献   

6.
The reaction between 1-pyrenecarboxaldehyde (C16H9CHO) and the labile triosmium cluster [Os3(CO)10(CH3CN)2] gives rise to the formation of two new compounds by competitive oxidative addition between the aldehydic group and an arene C-H bond, to afford the acyl complex [Os3(CO)10(μ-H)(μ-COC16H9)] (1) and the compound [Os3(CO)10(μ-H) (C16H8CHO)] (2), respectively. Thermolysis of [Os3(CO)10(μ-H)(μ-C16H9CO)] (1) in n-octane affords two new complexes in good yields, [Os3(CO)9(μ-H)2(μ-COC16H8)] (3) and the pyryne complex [Os3(CO)9(μ-H)23112-C16H8)] (4).In contrast, when 1-pyrenecarboxaldehyde reacts with [Ru3(CO)12] only one product is obtained, [Ru3(CO)9(μ-H)23112-C16H8)] (5), a nonacarbonyl cluster bearing a pyrene ligand. All compounds were characterized by analytical and spectroscopic data, and crystal structures for 1, 2, 4 and 5 were obtained.  相似文献   

7.
A new homonuclear and heterodinuclear pyridine-2,6-dicarboxylate complexes, formulated as (enH2)[Cu(dipic)2]·2.5H2O (1) and [Cu(μ-dipic)2Zn(H2O)5]·2H2O (2) (en = ethylenediamine, dipic = pyridine-2,6-dicarboxylate) were synthesized according the reactions between the three species of copper(II) and zinc(II) nitrate, ethylenediamine and pyridine-2,6-dicarboxylic acid. Complexes have been characterized by the methods of elemental, spectroscopic (IR and UV–Vis), thermal (TG/DTG, DTA) analysis, magnetic measurement and single crystal X-ray diffraction. Correlation coefficient, activation energies, E∗; pre-exponential factor, A; entropies, S∗; enthalpies, H∗ and Gibbs free energies, G∗ of the thermal decomposition reactions have been calculated under the derivations from thermogravimetric (TG) and differential thermogravimetric (DTG) curves, using the Coats–Redfern and Horowitz–Metzger methods. Complex 1 belonged to a six-coordinate behavior with a distorted octahedral geometry around Cu(II), that the structure contains two pyridine-2,6-dicarboxylate species as a tridentate ligands and ethylenediaminium cation as a counter ion as well as 2.5 uncoordinated water molecules. On the other hand complex 2 contains six-coordinated Cu(II) and Zn(II) ions, which are linked by two O atoms of the same carboxyl group from dipicolinic acid. The dipicolinate dianions again behave as tridentate ligands in 2. Two uncoordinated water molecules are also present in the structure. The structure units of 1 and 2 are mutually held by the hydrogen bonds and π?π interactions. There is also a C–O?π interaction in 2. The Cu(II) complexes are connected to one another via O–H?O hydrogen bonds, forming water clusters, which play an important role in the stabilization of the crystal structure. In the water clusters, the water molecules are trapped by the cooperative association of coordination interactions as well as hydrogen bonds.  相似文献   

8.
Ziessel R  Stroh C 《Organic letters》2003,5(14):2397-2400
[structure: see text] 2,6-Disubstituted pyridines, 6-substituted 2,2'-bipyridines, and 6,6'-disubstituted 2,2'-bipyridines are readily prepared under mild conditions from 5-(dimethylamino)-1-naphthalenesulfonamide chloride (DANS-Cl) and chloromethyl-nitronyl nitroxide (CH(2)Cl-NIT) starting materials and adequately functionalized building blocks. The syntheses of the pyridine molecules bearing two radicals and a DANS fragment first required the attachment of the aliphatic radical onto an aldehyde-protected dansylated compound, followed by the construction of the second aromatic radical.  相似文献   

9.
Redox potentials of photosensitive cyclometalated RuII derivatives of 2-phenylpyridine or 2-(4-tolyl)pyridine are controllably decreased by up to 0.8 V within several minutes. This is achieved by irradiation of the ruthena(II)cycles cis-[Ru(o-X-2-py)(LL)(MeCN)2]PF6 (2, X = C6H4 (a) or 4-MeC6H3 (b), LL = 1,10-phenanthroline or 2,2'-bipyridine). The cis geometry of the MeCN ligands has been confirmed by the X-ray structural studies. The sigma-bound sp2 carbon of the metalated ring is trans to LL nitrogen. Complexes 2 are made from [Ru(o-X-2-py)(MeCN)4]PF6 (1) and LL. This "trivial" ligand substitution is unusual because 1a reacts readily with phen in MeCN as solvent to give cis-[Ru(o-C6H4-2-py)(phen)(MeCN)2]PF6 (2c) in a 83% yield, but bpy does not afford the bpy-containing 2 under the same conditions. cis-[Ru(o-C6H4-2-py)(bpy)(MeCN)2]PF6 (2e) has been prepared in CH2Cl2 (74%). Studies of complexes 2c,e by cyclic voltammetry in MeOH in the dark reveal RuII/III quasy-reversible redox features at 573 and 578 mV (vs Ag/AgCl), respectively. A minute irradiation 2c and 2e converts them into new species with redox potentials of -230 and 270 mV, respectively. An exceptional potential drop for 2c is accounted for in terms of a photosubstitution of both MeCN ligands by methanol. ESR, 1H NMR, and UV-vis data indicate that the primary product of photolysis of 2c is an octahedral monomeric low-spin (S = 1/2) RuIII species, presumably cis-[RuIII(o-C6H4-2-py)(phen)(MeOH)2]2+. The primary photoproduct of bpy complex 2e is cis-[RuII(o-C6H4-2-py)(bpy)(MeCN)(MeOH)]+, and this accounts for a lower decrease in the redox potential. Irradiation of 2c in the presence of added chloride affords [(phen)(o-C6H4-2-py)ClRuIIIORuIVCl(o-C6H4-2-py)(phen)]PF6, a first mu-oxo-bridged mixed valent dimer with a cyclometalated unit. The structure of the dimer has been established by X-ray crystallography.  相似文献   

10.
The reactions of stoichiometric amounts of Cu(CH3COO)2 · 2H2O or Ni(CH3COO)2 · 2H2O with KHL (potassium salt of salicylideneglycine) and 4,4′-bipy or 2,2′-bipy ethanol afforded [Cu2(L)2(μ-4,4′-bipy)(4,4′-bipy)2] · 2H2O (1) (L = salicylideneglycine) and Ni(OAc)2(2,2′-bipy) (H2O)2 (2), respectively. The structure of 1 contains two Cu(II)'s, bridged by 4,4′-bipy; each copper is square pyramidal. Complex 2 contains a Ni(II) in highly distorted octahedral geometry. The two complexes were constructed into 3-D interwoven networks by typical H-bonding (i.e., O?H ··· O and N?H ··· O) and some other intra- or intermolecular weak interactions (i.e., C?H ··· O).  相似文献   

11.
Some mixed-valence Fe(II) Fe(III) complexes of thiocarboxylic acids and straight chain fatty acids with general formula [Fe(II)Fe(III)(2)O(SOCR)(6)(H(2)O)(3)] and [Fe(II)Fe(III)(2)O(SOCR)(3)(OOCR')(3)(CH(3)OH)(3)] (where, R=CH(3) or C(6)H(5) and R'=C(13)H(27), C(15)H(31) or C(17)H(35)) were synthesized and characterized by elemental analyses, spectral (infrared, electronic and M?ssbauer) studies, molar conductance and magnetic susceptibility measurements. The infrared spectra suggested bridging nature of carboxylate and thiocarboxylate anions along with upsilon(asym)(Fe(3)O) vibrations in the complexes. M?ssbauer studies revealed two resolved quadrupole doublets at 120-315 K confirming the presence of Fe(II) and Fe(III) moieties in the complexes. This was supported by the observed electronic spectral bands in the complexes at room temperature. The spectrum showed a band at around 13,800 cm(-1) which indicated an intervalence-transfer. Magnetic susceptibility measurements showed weak antiferromagnetic coupling related to mixed-valence pairs with S(2)=2, em leader S(1)=S(3)=5/2 spin exchange model. Conductance data indicated, the complexes were non-electrolytes in nitrobenzene. A structure has been established on the basis of these studies.  相似文献   

12.
13.
Treatment of [RuCl(2)(DMSO)(4)] with 2-aminoethanethiol (Haet) in ethanol gave a dicationic triruthenium complex, [Ru[Ru(aet)(3)](2)]Cl(2) ([1]Cl(2)). Complex [1]Cl(2) was also obtained by treatment of RuCl(3).nH(2)O with excess Haet in water. When [1](2+) was chromatographed on a cation-exchange column of SP-Sephadex C-25, meso (DeltaLambda) and racemic (DeltaDelta/LambdaLambda) isomers of the corresponding tricationic complex, [Ru[Ru(aet)(3)](2)](3+) ([2](3+)), were eluted with aqueous NaNO(3). The racemic isomer of [2](3+) was optically resolved into DeltaDelta and LambdaLambda isomers by using [Sb(2)(R,R-tartrato)(2)](2-) as a resolving agent. The molecular structures of DeltaLambda- and DeltaDelta/LambdaLambda-[2](NO(3))(3) were determined by X-ray crystallography. In these complexes, the central Ru atom is coordinated by six thiolato groups from two terminal fac-(S)-[Ru(aet)(3)] units in an octahedral geometry, forming a linear-type S-bridged triruthenium structure. The spectroelectrochemical studies on the electronic absorption and CD spectra, together with the electrochemical studies, demonstrated that [1](2+) and [2](3+) are interconvertible with each other through a one-electron redox process, retaining the chirality of the triruthenium structure. Their electronic structures were investigated on the basis of EPR and magnetic susceptibility measurements, which indicated that [1](2+) and [2](3+) have spin ground states of S(t) = 0 and S(t) = 1/2, respectively. The corresponding L-cysteinato complex, [Ru[Ru(L-cys-N,S)(3)](2)](3-), which was formed from RuCl(3).nH(2)O and excess L-cysteine (L-H(2)cys) in water followed by air oxidation, is also presented.  相似文献   

14.
The novel bridging ligand 1,8-bis(2,2':6',2"-terpyridyl)anthracene (btpyan) is synthesized by three reactions from 1,8-diformylanthracene to connect two [Ru(L)(OH)]+ units (L = 3,6-di-tert-butyl-1,2-benzoquinone (3,6-tBu2qui) and 2,2'-bipyridine (bpy)). An addition of tBuOK (2.0 equiv) to a methanolic solution of [RuII2(OH)2(3,6-tBu2qui)2(btpyan)](SbF6)2 ([1](SbF6)2) results in the generation of [RuII2(O)2(3,6-tBu2sq)2(btpyan)]0 (3,6-tBu2sq = 3,6-di-tert-butyl-1,2-semiquinone) due to the reduction of quinone coupled with the dissociation of the hydroxo protons. The resultant complex [RuII2(O)2(3,6-tBu2sq)2(btpyan)]0 undergoes ligand-localized oxidation at E1/2 = +0.40 V (vs Ag/AgCl) to give [RuII2(O)2(3,6-tBu2qui)2(btpyan)]2+ in MeOH solution. Furthermore, metal-localized oxidation of [RuII2(O)2(3,6-tBu2qui)2(btpyan)]2+ at Ep = +1.2 V in CF3CH2OH/ether or water gives [RuIII2(O)2(3,6-tBu2qui)2(btpyan)]4+, which catalyzes water oxidation. Controlled-potential electrolysis of [1](SbF6)2 at +1.70 V in the presence of H2O in CF3CH2OH evolves dioxygen with a current efficiency of 91% (21 turnovers). The turnover number of O2 evolution increases to 33,500 when the electrolysis is conducted in water (pH 4.0) by using a [1](SbF6)2-modified ITO electrode. On the other hand, the analogous complex [RuII2(OH)2(bpy)2(btpyan)](SbF6)2 ([2](SbF6)2) shows neither dissociation of the hydroxo protons, even in the presence of a large excess of tBuOK, nor activity for the oxidation of H2O under similar conditions.  相似文献   

15.
自六十年代以来陆续发现稀土化合物具有一系列特殊的药效作用 ,使稀土元素在药物上的应用展现出广阔前景。目前 ,已有不少稀土化合物应用于临床 ,如抗凝血药物 3 磺酸异烟酸钕、左旋糖酸镨、钕混合物 ;消炎药水杨酸钐等。合成具有生物活性配体的稀土配合物是寻找有效稀土药物的一条途径。瑞香素是一具有抗菌、抗炎、抗凝血等生物活性的香豆素类化合物 ,其分子结构为 :稀土与香豆素类的配合物的合成与性质研究己有不少报道[1,2 ] 。为了进一步研究这类配合物的性质和生物活性 ,我们合成了六种瑞香素稀土配合物。1 实验部分1 .1 仪器及试剂…  相似文献   

16.
17.
本文报道以卤代的卡拜化合物[Mo(≡CC~6H~5)Br(CO)~2(PY)~2](Py=吡啶)(1)为原料,分别与八羰基二钴、九羰基二铁和十羰基二锰反应,制得未见报道的三核原子簇合物[Co~2Mo(μ~3-CC~6H~5)Br(CO)~8(Ph)~2](2)、[Fe~2Mo(μ~3-CC~6H~5)(μ-CO)Br(CO)~8(Py)~2](3)和[Mn~2Mo(μ~3-CC~6H~5)Br(CO)~1~0(Py)~2](4)。但1与含钼钼三重键的化合物[(C~5H~5)~2Mo~2-(CO)~4]的加成反应未能实现。通过元素分析、IR、^1H和^1^3CNMR推断了2~4的结构。  相似文献   

18.
Reactions of oxo-centered triruthenium acetate complexes [Ru3O(OAc)6(py)2(CH3OH)](PF6) (py = pyridine, OAc = CH3COO-) (1) with nearly equimolar amounts of dppa [bis(diphenylphosphino)acetylene] or dppen [trans-1,2-bis(diphenylphosphino)ethylene] gave [Ru3O(OAc)6(py)2(L)](PF6) (L = dppa, 2; dppen, 3). With 2.4 equiv of 1, the reactions provided diphosphine-linked triruthenium dimers, [[Ru3O(OAc)6(py)2]2(L)](PF6)2 (L = dppa, 4; L = dppen, 5), respectively. Similarly, the reactions of [Ru3O(OAc)6(L')2(MeOH)]+ [L' = dmap (4-(dimethylamino)pyridine), 1a; L' = abco (1-azabicyclo[2.2.2]octane), 1b] with dppen gave dppen-linked dimers, [[Ru3O(OAc)6(dmap)2]2(dppen)](SbF6)2 (6) and [[Ru3O(OAc)6(abco)2]2(dppen)](BF4)2 (7), respectively. The chemical reduction of 2, 4, and 5 by hydrazine afforded one- or two-electron-reduced, neutral products, Ru3O(OAc)6(py)2(dppa) (2a), [Ru3O(OAc)6(py)2]2(dppa) (4a), and [Ru3O(OAc)6(py)2]2(dppen) (5a), respectively. The complexes were characterized by elemental analyses, ES-MS, UV-vis, IR, and 31P NMR spectroscopies, and cyclic and differential-pulse voltammetries. The molecular structures of compounds 2, 4, 5, 5a, 6, and 7 were determined by single-crystal X-ray diffraction. In 0.1 M (Bu4N)PF6-acetone, the monomers and dimers of triruthenium clusters show reversible and multistep redox responses. The two triruthenium cluster centers in dimers undergo stepwise reductions and oxidations due to the identical redox processes of the individual Ru3O cluster cores, suggesting the presence of electronic communications between them through the conjugated diphosphine spacer. The redox wave splitting mediated by dppa containing an ethynyl group (C triple bond C) is found to be more extensive than that by dppen containing an ethenyl (C=C) one. It appears that the redox wave splitting is enhanced by the introduction of electron-donating substituents on the auxiliary pyridine rings.  相似文献   

19.
Three novel thiocyanate supramolecular compounds have been synthesized and characterized by X-ray diffraction and fluorescent spectra. Compound [pipH]2[Co(NCS)4] (pip=piperazine) 1 possesses a two-dimensional layer connected by the combination of N-H?N hydrogen bonds and weak S?S contacts. Under the same conditions, using nickel salt instead of cobalt salt as a starting material, we obtained a different two-dimensional supramolecular layer [pipH]2[Ni(NCS)4] 2 connected by unusual N-H?S hydrogen bonds and weak S?S contacts. In order to observe the influence of the dimension of ligand on the self-assembly structure, dabco was used for substituting pip, and compound [dabcoH]2[Ni(NCS)4] (dabco=1,4-Diazabicyclo[2.2.2] octane) 3 was gained, which constructed two-dimensional, highly wavy network with hourglass-shaped cavities only through N-H?S hydrogen bonds.  相似文献   

20.
《Tetrahedron letters》1987,28(1):55-58
An efficient electrosynthesis of homoallyl alcohols or β-hydroxy esters in the presence of catalytic amounts of the NiBr2(2,2′-bipyridine) complex has been developped from mixed electrolysis of methallylchloride, or methylchloroacetate with several carbonyl compounds, using a one-compartment cell equiped of a sacrificial zinc anode.  相似文献   

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