Synthesis, Structure and Characterization of a New 1D Coordination Polymer:[Pb(L)(cis-1,4-chdc)]·0.5H2O

A new 1D coordination polymer, [Pb(L)(cis-1,4-chdc)]·0.5H2O (cis-1,4-chdc = 1,4-cyclohexanedicarboxylate and L = 2-(4-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), has been synthesized under hydrothermal conditions and characterized by elemental analysis, TG and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.153(5), b = 10.338(5), c = 13.074(5), α = 80.956(5), β = 89.725(5), γ = 80.534(5)°, V = 1204.8(10)3 , Z = 1, C54H44F2N8O9Pb2 , Mr = 1401.35, Dc = 1.931 g/cm3 , F(000) = 678, μ(MoKa) = 7.055 mm-1 , R = 0.0277 and wR = 0.0559. Each cis-1,4-chdc anion coordinates with two Pb(Ⅱ) atoms in a bis-chelating coordination mode. In this way, cis-1,4-chdc anions bridged the neighboring Pb(Ⅱ) atoms to generate a 1D chain structure. The L ligands from neighboring chains are paired through the strong π-π interactions to generate a fascinating 2D supramolecular layer.     

Synthesis and Structure of a Novel Supramolecular Compound [Co(2,2''-bipy)(H2 O)4 ][trans-1,4-chdc] and Separation of Isomer of 1,4-Cyclohexanedicarboxylic Acid

A supramolecular compound, [Co(2,2'-bipy)(H2O)4][trans-1,4-chdc] (compound 1) (2,2'-bipy=2,2'-bipyridine, 1,4-chdcH2=1,4-cyclohexanedicarboxylic acid), was synthesized and characterized by single-crystal X-ray diffraction analysis, IR spectrometry, TG analysis, and elemental analyses. Single-crystal X-ray diffraction analysis revealed that [Co(2,2'-bipy)(H2O)4]2 units and adjacent 1,4-chdc2- formed a single layer by hydrogen bonding and electrostatic interactions along the ac-plane, and two symmetry-related single layers interacted with each other by hydrogen bonding, resulting in a double layer, which further formed a 3-D structure by π-π stacking. The most attractive structural feature of compound 1 is that 1,4-chdc2- possesses only trans-conformation although there are both cis- and trans-conformations in the raw material.     

基于三核镉的二维金属有机骨架[Cd_3(L)_2(cis-1,4-chdc)_2(trans-1,4-chdc)]的合成、结构和表征(英文)

The title metal-organic framework, [Cd3(L)2(cis-1,4-chdc)2(trans-1,4-chdc)] (1, L=2-(4-fluorophenyl)-1H-imidazo [4,5-f][1,10]phenanthroline, 1,4-H2chdc=1,4-cyclohexanedicarboxylic acid) has been synthesized under hydrothermal condition and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a=0.851 71(17) nm, b=1.199 9(2) nm, c=1.521 4(3) nm, α=68.13(3)°, β=79.48(3)°, γ=82.32(3)°, V=1.415 0(5) nm3, Z=1, C62H52Cd3F2N8O12, Mr=1 476.32, Dc=1.732 g·cm-3, F(000)=738, μ(Mo Kα)=1.197 mm-1, R=0.067 6 and wR=0.135 4. The cis-1,4-chdc2- ligands bridge the Cd(Ⅱ) cations to form a trinuclear Cd(Ⅱ) based double chain along the a axis. Further, the trans-chdc2- ligands link the adjacent double chains to yield an interesting two-dimensional network. The L ligands are attached on both sides of the layers.     

Bis(acetylacetonato)ruthenium(II) complexes containing alkynyldiphenylphosphines. Formation and redox behaviour of [Ru(acac)2(Ph2PC triple bond CR)2] (R=H, Me, Ph) complexes and the binuclear complex cis-[{Ru(acac)2}2(micro-Ph2PC triple bond CPPh2)}2

Two equivalents of Ph(2)PC triple bond CR (R=H, Me, Ph) react with thf solutions of cis-[Ru(acac)(2)(eta(2)-alkene)(2)] (acac=acetylacetonato; alkene=C(2)H(4), 1; C(8)H(14), 2) at room temperature to yield the orange, air-stable compounds trans-[Ru(acac)(2)(Ph(2)PC triple bond CR)(2)] (R=H, trans-3; Me=trans-4; Ph, trans-5) in isolated yields of 60-98%. In refluxing chlorobenzene, trans-4 and trans-5 are converted into the yellow, air-stable compounds cis-[Ru(acac)(2)(Ph(2)PC triple bond CR)(2)] (R=Me, cis-4; Ph, cis-5), isolated in yields of ca. 65%. From the reaction of two equivalents of Ph(2)PC triple bond CPPh(2) with a thf solution of 2 an almost insoluble orange solid is formed, which is believed to be trans-[Ru(acac)(2)(micro-Ph(2)PC triple bond CPPh(2))](n) (trans-6). In refluxing chlorobenzene, the latter forms the air-stable, yellow, binuclear compound cis-[{Ru(acac)(2)(micro-Ph(2)PC triple bond CPPh(2))}(2)] (cis-6). Electrochemical studies indicate that cis-4 and cis-5 are harder to oxidise by ca. 300 mV than the corresponding trans-isomers and harder to oxidise by 80-120 mV than cis-[Ru(acac)(2)L(2)] (L=PPh(3), PPh(2)Me). Electrochemical studies of cis-6 show two reversible Ru(II/III) oxidation processes separated by 300 mV, the estimated comproportionation constant (K(c)) for the equilibrium cis-6(2+) + cis6 <=> 2(cis-6(+)) being ca. 10(5). However, UV-Vis spectra of cis-6(+) and cis-6(2+), generated electrochemically at -50 degrees C, indicate that cis-6(+) is a Robin-Day Class II mixed-valence system. Addition of one equivalent of AgPF(6) to trans-3 and trans-4 forms the green air-stable complexes trans-3 x PF(6) and trans-4 x PF(6), respectively, almost quantitatively. The structures of trans-4, cis-4, trans-4 x PF(6) and cis-6 have been confirmed by X-ray crystallography.     

Facile cyanamide-ammonia coupling mediated by cis- and trans-[PtIIL2] centers and giving metal-bound guanidines

Diffusion of ammonia into CH(2)Cl(2) solutions of the dialkylcyanamide complexes cis- or trans-[PtCl(2)(RCN)(2)] (R = NMe(2), NEt(2), NC(5)H(10)) at 20-25 degrees C leads to metal-mediated cyanamide-ammonia coupling to furnish, depending on reaction time, one or another type of novel bisguanidine compound, i.e. the molecular cis- or trans-[PtCl(2){NH=C(NH(2))R}(2)] (cis- and trans-) and the cationic cis- or trans-[Pt(NH(3))(2){NH=C(NH(2))R}(2)](Cl)(2) (cis- and trans-) complexes. Compounds cis- or trans- were converted to cis- or trans-, accordingly, upon prolonged treatment with NH(3) in CH(2)Cl(2). The ammination of the relevant nitrile complexes cis- or trans-[PtCl(2)(RCN)(2)] (R = Et, CH(2)Ph, Ph) in CH(2)Cl(2) solutions affords only the cationic compounds cis- or trans-[Pt(NH(3))(2){NH=C(NH(2))R}(2)](Cl)(2) (cis- and trans-). The formulation of was supported by satisfactory C, H and N elemental analyses, agreeable ESI(+)-MS (or FAB(+)-MS), IR, (1)H and (13)C NMR spectroscopies. The structures of trans-, trans-, cis-, trans-, cis-, and cis- were determined by single-crystal X-ray diffraction disclosing structural features and showing that the ammination gives ligated guanidines and amidines in the E- and Z-forms, respectively, where both correspond to the trans-addition of NH(3) to the nitrile species.     

Cu(I) complexes based on cis, cis-1,3,5-tris(arylideneamino)cyclohexane ligands: synthesis, structure and CO binding

A new series of sterically bulky, facially coordinating N(3)-donor tach-based ligands (tach; cis,cis-1,3,5-triaminocyclohexane) [2.1; cis,cis-1,3,5-tris(2,4-dimethylbenzylideneamino)cyclohexane, 4.1; cis,cis-1,3,5-tris(pentamethylbenzylideneamino)cyclohexane, 5.1; cis,cis-1,3,5-tris(2,6-dimethoxybenzylideneamino)cyclohexane, 6.1; cis,cis-1,3,5-tris(pentafluorobenzylideneamino)cyclohexane, 7.1; cis,cis-1,3,5-tris(3,5-bis(ditrifluoromethyl)benzylideneamino)cyclohexane, 8.1; cis,cis-1,3,5-tris(2-trifluoromethylbenzylideneamino)cyclohexane, 9.1; cis,cis-1,3,5-tris(2-methoxybenzylideneamino)cyclohexane] have been obtained from the condensation of tach with three equivalents of the appropriate substituted benzaldehyde. Reaction with [Cu(NCCH(3))(4)]PF(6) gives Cu(I) complexes of tach-based ligands {2.2-9.2, eg; 2.2; [Cu(2.1)(NCCH(3))]PF(6)}. Displacement of the acetonitrile ligand by CO was achieved successfully for all the Cu(I) complexes of tach-based ligands and the resulting complexes have been shown to bind carbon monoxide {2.3-9.3, eg; 2.3; [Cu(2.1)(CO)]PF(6)}. The X-ray single crystal structures of 5.1, 8.1, 9.1, 3.2, 7.2, 8.2, 9.2, 3.3, 5.3 and 6.3 have been determined.     

Synthesis and Crystal Structure of a New Mixed-ligand Nickel（Ⅱ） Coordination Polymer： [Ni（L）（cis-1,4-chdc）]n·1.25nH2O

A new one-dimensional Ni(II) coordination polymer [Ni(L)(cis-1,4- chdc)]n?1.25nH2O has been synthesized under hydrothermal conditions by using 1,4-cyclohexanedicarboxylic acid (1,4-H2chdc) and 2-(3-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (L). Crystallographic data for the compound: triclinic, space group P with a=8.777(2), b=10.662(2), c=13.799(3), α=89.480(4), β=73.933(3), γ=81.980(4)°, V=1228.2(5)3, Z=2, C27H22.50FN4NiO5.25, Mr=568.70, Dc=1.527 g/cm3, F(000)=583, μ(MoKa)=0.846 mm-1, R=0.0634 and wR=0.1465. Neighboring Ni(II) atoms are linked by the cis-1,4-chdc ligands to generate a one-dimensional chain structure. The π-π interactions between the L ligands of neighboring chains led to the formation of a two-dimensional supramolecular layer. The elemental analysis, IR spectrum and TG of the compound have been studied.     

Probing single-chain magnets in a family of linear chain compounds constructed by magnetically anisotropic metal-ions and cyclohexane-1,2-dicarboxylate analogues

Five new metal-carboxylate chain-based laminated compounds, namely, infinity2[FeII(e,e-trans-1,2-chdc)] (3) (1,2-chdc = cyclohexane-1,2-dicarboxylate), infinity2[NiII(mu-OH2)(e,a-cis-1,2-chdc)] (4), infinity2[CoII(mu-OH2)(1,2-chedc)] (5) (1,2-chedc = cyclohex-1-ene-1,2-dicarboxylate), infinity2[Co5II(mu3-OH)2(OH2)2(1,2-chedc)4] (6), and infinity2[CoII(4-Me-1,2-chdc)] (7) (4-Me-1,2-chdc = trans-4-methylcyclohexane-1,2-dicarboxylate) have been hydrothermally synthesized. In these series of magnetic chain-based compounds, 3 and 7 have the same dimeric paddle-wheel M(II)-carboxylate chain as the previously reported compound, infinity2[CoII(trans-1,2-chdc)] (2). However, compound 3 does not behave as a single-chain magnet (SCM) but simply an alternating ferro-antiferro magnetic chain. Compound 4 has the cis conformation of 1,2-chdc ligand, which leads to a uniform aqua-carboxylate-bridged Ni(II) chain. Such a Ni-O chain exhibits strong antiferromagnetic interactions, leading to a diamagnetic ground state. Compound 5 features a corner-sharing triangular chain, or delta-chain, which is part of a Kagom lattice. However, 5 does not exhibit a spin-frustrated effect but simply spin competition. Compound 6 has a unique pentanuclear CoII cluster, which is further connected by the syn-anti carboxylate into a chain structure. Compound 6 exhibits antiferromagnetic interactions among the Co(II) ions, and no SCM behavior is observed. These results might indicate that the dimeric paddle-wheel Co(II)-carboxylate chain is essential in obtaining SCM behavior in this family of compounds. Although 2 and 7 have very similar SCM behavior, alternating current magnetic studies show that 7 has a higher energy barrier than that of 2. Such behavior is probably caused by the larger anisotropic energy barrier in 7.     

Syntheses, characterization, and dioxygen reactivities of Cu(I) complexes with cis,cis-1,3,5-triaminocyclohexane derivatives: a Cu(III)2O2 intermediate exhibiting higher C-H activation

Six Cu(I) complexes with cis,cis-1,3,5-triaminocyclohexane derivatives (R3CY, R = Et, iBu, and Bn), [Cu(MeCN)(Et3CY)]SbF6 (1), [Cu(MeCN)(iBu3CY)]SbF6 (2), [Cu(MeCN)(Bn3CY)]SbF6 (3), [Cu(CO)(Et3CY)]SbF6 (4), [Cu(CO)(iBu3CY)]SbF6 (5), and [Cu(CO)(Bn3CY)]SbF6 (6), were prepared to probe the ability of copper complexes to effectively catalyze oxygenation reactions. The complexes were characterized by elemental analysis, electrochemical and X-ray structure analyses, electronic absorption spectroscopy, IR spectroscopy, 1H NMR spectroscopy, and ESI mass spectrometry. The crystal structures of 1-3 and 6 and the CO stretching vibrations (nuCO) of 4-6 demonstrate that the ability of R3CY to donate electron density to the Cu(I) atom is stronger than that of the previously reported ligands, 1,4,7-triazacyclononane (R3TACN) and 1,4,7-triazacyclodecane (R3TACD). Reactions of complexes 1-3 with dioxygen in THF or CH2Cl2 at -105 to -80 degrees C yield bis(mu-oxo)dicopper(III) complexes 7-9 as intermediates as confirmed by electronic absorption spectroscopy and resonance Raman spectroscopy. The Cu-O stretching vibrations, nu(Cu-O) for 7 (16O2: 553, 581 cm-1and 18O2: 547 cm-1) and 8 (16O2: 571 cm-1 and 18O2: 544 cm-1), are observed in a lower energy region than previously reported for bis(micro-oxo) complexes. The decomposition rates of complexes 7-9 in THF at -90 degrees C are 2.78 x 10-4 for 7, 8.04 x 10-4 for 8, and 3.80 x 10-4 s-1 for 9. The decomposition rates of 7 and 8 in CH2Cl2 were 5.62 x 10-4 and 1.62 x 10-3 s-1, respectively, and the thermal stabilities of 7-9 in CH2Cl2 are lower than the values measured for the complexes in THF. The decomposition reactions obeyed first-order kinetics, and the H/D isotope experiments for 8 and 9 indicate that the N-dealkylation reaction is the rate-determining step in the decomposition processes. On the other hand, the decomposition reaction of 7 in THF results in the oxidation of THF (acting as an exogenous substrate) to give 2-hydroxy tetrahydrofuran and gamma-butyrolactone as oxidation products. Detailed investigation of the N-dealkylation reaction for 8 by kinetic experiments using N-H/D at -90 degrees C showed a kinetic isotope effect of 1.25, indicating that a weak electrostatic interaction between the N-H hydrogen and mu-oxo oxygen contributes to the major effect on the rate-determining step of N-dealkylation. X-ray crystal structures of the bis(micro-hydroxo)dicopper(II) complexes, [Cu2(OH)2(Et3CY)2](CF3SO3)2 (10), [Cu2(OH)2(iBu3CY)2](CF3SO3)2 (11), and [Cu2(OH)2(Bn3CY)2](ClO4)2 (12), which have independently been prepared as the final products of bis(micro-oxo)dicopper(III) intermediates, suggest that an effective interaction between N-H and mu-oxo in the Cu(III)2(micro-O)2 core may enhance the oxidation ability of the metal-oxo species.     

Biologically active platinum complexes containing 8-thiotheophylline and 8-(methylthio)theophylline

Complexes [Pt(mu-N,S-8-TT)(PPh(3))(2)](2) (1), [Pt(mu-S,N-8-TT)(PTA)(2)](2) (2), [Pt(8-TTH)(terpy)]BF(4) (3), cis-[PtCl(8-MTT)(PPh(3))(2)] (4), cis-[Pt(8-MTT)(2)(PPh(3))(2)] (5), cis-[Pt(8-MTT)(8-TTH)(PPh(3))(2)] (6), cis-[PtCl(8-MTT)(PTA)(2)] (7), cis-[Pt(8-MTT)(2)(PTA)(2)] (8), and trans-[Pt(8-MTT)(2)(py)(2)] (9) (8-TTH(2) = 8-thiotheophylline; 8-MTTH = 8-(methylthio)theophylline; PTA = 1,3,5-triaza-7-phosphaadamantane) are presented and studied by IR and multinuclear ((1)H, (31)P[(1)H]) NMR spectroscopy. The solid-state structure of 4 and 9 has been authenticated by X-ray crystallography. Growth inhibition of the cancer cells T2 and SKOV3 induced by the above new thiopurine platinum complexes has been investigated. The activity shown by complexes 4 and 9 was comparable with cisplatin on T2. Remarkably, 4 and 9 displayed also a valuable activity on cisplatin-resistant SKOV3 cancer cells.     

Trans --> cis isomerization of trans-[(dppm)2Ru(H)(L)][BF4] (L = P(OR)3) complexes: preparation of cis-[(dppm)2Ru(eta2-H2)(L)][BF4]2

A series of new dicationic dihydrogen complexes of ruthenium of the type cis-[(dppm)(2)Ru(eta(2)-H(2))(L)][BF(4)](2) (dppm = Ph(2)PCH(2)PPh(2); L = P(OMe)(3), P(OEt)(3), PF(O(i)Pr)(2)) have been prepared by protonating the precursor hydride complexes cis-[(dppm)(2)Ru(H)(L)][BF(4)] (L = P(OMe)(3), P(OEt)(3), P(O(i)Pr)(3)) using HBF(4).Et(2)O. The cis-[(dppm)(2)Ru(H)(L)][BF(4)] complexes were obtained from the trans hydrides via an isomerization reaction that is acid-accelerated. This isomerization reaction gives mixtures of cis and trans hydride complexes, the ratios of which depend on the cone angles of the phosphite ligands: the greater the cone angle, the greater is the amount of the cis isomer. The eta(2)-H(2) ligand in the dihydrogen complexes is labile, and the loss of H(2) was found to be reversible. The protonation reactions of the starting hydrides with trans PMe(3) or PMe(2)Ph yield mixtures of the cis and the trans hydride complexes; further addition of the acid, however, give trans-[(dppm)(2)Ru(BF(4))Cl]. The roles of the bite angles of the dppm ligand as well as the steric and the electronic properties of the monodentate phosphorus ligands in this series of complexes are discussed. X-ray crystal structures of trans-[(dppm)(2)Ru(H)(P(OMe)(3))][BF(4)], cis-[(dppm)(2)Ru(H)(P(OMe)(3))][BF(4)], and cis-[(dppm)(2)Ru(H)(P(O(i)Pr)(3))][BF(4)] complexes have been determined.     

Si-H and Si-Si activation at Pt: synthesis and reactivity of neutral and cationic silyl complexes

Reactions of [Pt(PEt(3))(3)] (1) with the silanes HSiPh(3), HSiPh(2)Me and HSi(OEt)(3) led to the products of oxidative addition, cis-[Pt(H)(SiPh(3))(PEt(3))(2)] (2), cis-[Pt(H)(SiPh(2)Me)(PEt(3))(2)] (3), cis-[Pt(H){Si(OEt)(3)}(PEt(3))(2)] (cis-4) and trans-[Pt(H){Si(OEt)(3)}(PEt(3))(2)] (trans-4). The complexes cis-4 and trans-4 can also be generated by hydrogenolysis of (EtO)(3)SiSi(OEt)(3) in the presence of 1. Furthermore, the silyl compounds cis-4 and trans-4 react with B(C(6)F(5))(3) and CH(3)CN by hydride abstraction to give the cationic silyl complex trans-[Pt{Si(OEt)(3)}(NCCH(3))(PEt(3))(2)][HB(C(6)F(5))(3)] (8). In addition, the reactivity of the complexes cis-4, trans-4 and 8 towards alkenes and CO was studied using NMR experiments.     

Assembly and properties of transition-metal coordination polymers based on semi-rigid bis-pyridyl-bis-amide ligand: effect of polycarboxylates on the dimensionality

Seven new coordination polymers, [Co()(1,3-BDC)(H(2)O)(3)]·H(2)O (), [Co()(1,2-BDC)(H(2)O)]·H(2)O (), [Co(3)()(1,2,4-BTC)(2)(H(2)O)(4)]·4H(2)O (), [Co()(NPH)]·2H(2)O (), [Cu()(1,3-BDC)] (), [Cu()(1,2-BDC)] (), [Cu()(1,3,5-HBTC)(H(2)O)](2)·2H(2)O () ( = N,N'-bis(pyridin-3-yl)cyclohexane-1,4-dicarboxamide, 1,3-H(2)BDC = 1,3-benzenedicarboxylic acid, 1,2-H(2)BDC = 1,2-benzenedicarboxylic acid, 1,2,4-H(3)BTC = 1,2,4-benzenetricarboxylic acid, H(2)NPH = 3-nitrophthalic acid and 1,3,5-H(3)BTC = 1,3,5-benzenetricarboxylic acid) have been hydrothermally synthesized by assembling transition-metal cobalt-copper salts with semi-rigid bis-pyridyl-bis-amide ligand and different aromatic polycarboxylic acids. Complex exhibits a one-dimensional (1D) sinusoidal-like chain, which is further assembled into a three-dimensional (3D) supramolecular framework through hydrogen-bonding interactions. Complex possesses a 3D framework with 4-connected 6(6) topology, which contains a two-dimensional (2D) distorted asymmetric hexagonal grid. When 1,2,4-BTC is used in complex , a 3D framework with (6(3)·8(2)·10)(2)(6(5)·8)(2)(8) topology is constructed. Complex possesses a 3D framework with 4-connected 6(6) topology, which is similar to that of except for containing a 2D symmetric hexagonal grid. When Co(II) ion is replaced by Cu(II) ion, the 3D framework of complex with (4·6(2))(4·6(6)·8(3)) topology based on and 1,3-BDC ligands is obtained. Complex shows a 2D cross network consisting of a superposed Cu- 1D chain and 1,2-BDC, which is further expanded into a 3D supramolecular framework by hydrogen-bonding interactions. In complex , 1,3,5-HBTC is employed as the auxiliary ligand, and a 3D supramolecular framework based on the undulated 2D layers is formed through π-π stacking and hydrogen-bonding interactions. Both the metal ions and polycarboxylates play important roles in the construction of the title complexes. In addition, the electrochemical behaviors and the fluorescence properties of the seven complexes have been investigated.     

Mn(II) Coordination Polymers Based on Bi-, Tri-, and Tetranuclear and Polymeric Chain Building Units: Crystal Structures and Magnetic Properties

Five new Mn(II) coordination polymers, namely [Mn(2)(tbip)(2)(bix)] (1), [Mn(3)(tbip)(3)(bix)(2)] (2), [Mn(3)(tbip)(2)(Htbip)(2)(bib)(2)]·4H(2)O (3), [Mn(4)(tbip)(4)(bbp)(2)(H(2)O)(2)] (4), and [Mn(4)(tbip)(4)(bip)]·2H(2)O (5), were prepared by hydrothermal reactions of Mn(II) acetate with H(2)tbip (5-tert-butyl isophthalic acid) in the presence of different di-imidazolyl coligands (bix =1,4-bis(imidazol-1-ylmethyl)benzene, bib =1,4-bis(imidazol) butane, bbp =1,3-bis(benzimidazol)propane, bip =1,3-bis(imidazol)propane). All complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, single-crystal X-ray crystallography, and powder X-ray diffraction. Single crystal X-ray studies show that these coordination polymers contain homometallic clusters varying from dimeric, trimeric, and tetrameric motifs to polymeric chains depending upon the coligands used. Complex 1 has a 3D 6-connected polycatenane network with dinuclear [Mn(2)O(2)] secondary building units. Complex 2 possesses a 3D 8-connected structure with trinuclear [Mn(3)(COO)(6)] units. Complex 3 shows a 3D pcu net based on trinuclear [Mn(3)(COO)(6)] clusters as nodes. Complex 4 features a 3D 8-connected structure constructed from the distorted square-grid tetranuclear [Mn(4)(μ(2)-COO)(8)(μ(2)-H(2)O)] units. Complex 5 shows a 3D (4,5,6)-connected net containing 1D μ-O/μ-COO alternately bridged chains. Magnetic susceptibility measurements indicate that complexes 1 and 3-5 show weak antiferromagnetic interactions between the adjacent Mn(II) ions, whereas 2 is a three-spin center homometallic ferromagnetic system.     

线型1,2-邻二萘醌-1-肟(1-nqo)钌配合物的合成

报道了含C_(16)长碳链线型1,2-邻二萘醌-1-肟(1-nqo)钌配合物trans-，cis- 及cis-，cis-[Ru(1-nqo)_2(CO)(spy)] (3)及(4)含C_(18)长碳链线型1-nqo钌配合 物cis-，cis-[Ru(1-nqo)_2(CO)(opy)] (5)，trans-，trans-[Ru(1-nqo)_2(opy) _2] (6)的合成。利用红外、FAB质谱、核磁共振氢谱及紫外-可见吸收光谱表征配 合物的结构，利用~1H-~1H偶合二维核磁技术对核磁共振峰进行指认。     

Hydrolytic metal-mediated coupling of dialkylcyanamides at a Pt(IV) center giving a new family of diimino ligands

Addition of excess R(2)NCN to an aqueous solution of K(2)[PtCl(4)] led to the precipitation of [PtCl(2)(NCNR(2))(2)] (R(2) = Me(2) 1; Et(2) 2; C(5)H(10) 3; C(4)H(8)O, 4) in a cis/trans isomeric ratio which depends on temperature. Pure isomers cis-1-3 and trans-1-3 were separated by column chromatography on SiO(2), while trans-4 was obtained by recrystallization. Complexes cis-1-3 isomerize to trans-1-3 on heating in the solid phase at 110 degrees C; trans-1 has been characterized by X-ray crystallography. Chlorination of the platinum(II) complexes cis-1-3 and trans-1-4 gives the appropriate platinum(IV) complexes [PtCl(4)(NCNR(2))(2)] (cis-5-7 and trans-5-8). The compound cis-6 was also obtained by treatment of [PtCl(4)(NCMe)(2)] with neat Et(2)NCN. The platinum(IV) complex trans-[PtCl(4)(NCNMe(2))(2)] (trans-5) in a mixture of undried Et(2)O and CH(2)Cl(2) undergoes facile hydrolysis to give trans-[PtCl(4)[(H)=C(NMe(2))OH](2)] (9; X-ray structure has been determined). The hydrolysis went to another direction with the cis-[PtCl(4)(NCNR(2))(2)] (cis-5-7) which were converted to the metallacycles [PtCl(4)[NH=C(NR(2))OC(NR(2))=NH]] (11-13) due to the unprecedented hydrolytic coupling of the two adjacent dialkylcyanamide ligands giving a novel (for both coordination and organic chemistry) diimino linkage. Compounds 11-13 and also 14 (R(2) = C(4)H(8)O) were alternatively obtained by the reaction between cis-[PtCl(4)(MeCN)(2)] and neat undried NCNR(2). The structures of complexes 11, 13, and 14 were determined by X-ray single-crystal diffraction. All the platinum compounds were additionally characterized by elemental analyses, FAB mass-spectrometry, and IR and (1)H and (13)C[(1)H] NMR spectroscopies.     

Facially coordinating cyclic triamines, part I. The coordination chemistry of cis-3,5-diaminopiperidine and substituted derivatives

An efficient and convenient method for the preparation of cis-3,5-diaminopiperidine (dapi) has been established and the coordination chemistry of this ligand with CoII, CoIII, NiII, CuII, ZnII, and CdII has been investigated in the solid state and in aqueous solution. Potentiometric measurements revealed a generally high stability for the bis complexes of the divalent cations with maximum stability for NiII (log beta2 = 21.2, beta2 = [M(dapi)2][M](-1)[dapi](-2), 25 degrees C, mu = 0.1 mol dm(-3)). Cyclic voltammetry established quasi-reversible formation of [Ni(dapi)2]3+ with a redox potential of 0.91 V (versus NHE) for the Ni(II/III) couple. [Co(dapi)2]3+ was prepared by aerial oxidation of the corresponding CoII precursor. The two isomers trans-[Co(dapi)2]3+ (1(3+), 26%) and cis-[Co(dapi)2]3+ (2(3+), 74%), have been separated and isolated as solid Cl- and CF3SO3- salts. In a non-aqueous medium 1(3+) and 2(3+) reacted with paraformaldehyde and NEt3 to give the methylidene-imino derivatives 3(3+) and 4(3+), in which the two piperidine rings are bridged by two or one N-CH2-O-CH2-N bridges, respectively. Crystal structure analyses were performed for H3dapi[ZnCl4]Cl, 1Cl3 x 2H2O, 2Cl3 x H2O, 3[ZnCl4]Cl, 4[ZnCl4]Cl, [Ni(dapi)2]Cl2 x H2O, [Cu(dapi)2](NO3)2, [Cu(dapi)Cl2], [(dapi)ClCd-(mu2-Cl)2-CdCl(dapi)], and [Co(dapi)(NO2)(CO3)]. The stability of [M(II)(dapi)]2+ and [M(II)(dapi)2]2+ complexes in aqueous solution, particularly the remarkably high tendency of [M(dapi)]2+ to undergo coordinative disproportionation is discussed in terms of the specific steric requirements of this ligand. Molecular mechanics calculations have been performed to analyze the different types of strain in these complexes. A variety of alkylated derivatives of dapi have been prepared by reductive alkylation with formaldehyde, benzaldehyde, salicylaldehyde, and pyridine-2-carbaldehyde. The NiII complexes of the pentadentate N3,N5-bis(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py2dapi) and the hexadentate N3,N5,1-tris(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py3dapi) have been isolated as crystalline ClO4- salts [Ni(py2dapi)Cl]ClO4 and [Ni(py3dapi)](ClO4)2 x H2O and characterized by crystal structure analyses.     

Metal-organic frameworks from homometallic chains of nickel(II) and 1,4-cyclohexanedicarboxylate connectors: ferrimagnet-ferromagnet transformation

The hydrothermal reactions of nickel(II) nitrate with a mixture of the geometric cis and trans isomers of 1,4-cyclohexanedicarboxylic acid (1,4-chdc or C6H10(COOH)2) and a base yield three structurally different complexes, [Ni3(mu3-OH)2(mu4-cis-1,4-chdc)2(H2O)4].2H2O (1), [Ni(3)(mu3-OH)2(mu4-trans-1,4-chdc)2(H2O)4].4H2O (2), and [Ni(H2O)4(mu2-trans-1,4-chdc)], depending on the reaction conditions. The single-crystal X-ray structure analyses of 1 and 2 reveal segregation of the isomers and formation of frameworks based on infinite Ni3(OH)2(H2O)4 chains, acting as secondary building units, connected by either cis- or trans-chdc for 1 and 2, respectively. The frameworks sustain channels that house two or four water molecules, respectively, according to the size and shape of the channels that depend on the particular isomer. The structure of 3 consists of chains of square-planar Ni(H2O)4 bridged by trans-chdc. Magnetic data as a function of temperature and field of the virgin samples for 1 indicate long-range ordering (LRO) to a ferrimagnetic ground state at 2.1 K that is reversibly transformed into a ferromagnet below 4.4 K upon partial dehydration and rehydration. Powder X-ray diffraction of 1, in its virgin state, after dehydration and after rehydration, confirms the stability of the framework. The magnetic data for 2 tend toward a LRO state to possibly a ferrimagnet below 2 K. The temperature dependence of the susceptibility of the two compounds is accounted for by the presence of both ferro- and antiferromagnetic exchanges within each chain via Ni-O-Ni and Ni-O-C-O-Ni pathways and weak coupling between neighboring chains via the 1,4-chdc unit. 3 is a uniform s = 1 antiferromagnetic chain (J/kB = 2.27(1) K).     

Determination of the structures of antiinflammatory copper(II) dimers of indomethacin by multiple-scattering analyses of X-ray absorption fine structure data

Copper K-edge X-ray absorption spectroscopic (XAS) measurements were recorded for the veterinary antiinflammatory Cu(II) complexes of indomethacin (1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid = IndoH), of the general formula [Cu(2)(Indo)(4)L(2)] (L = N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), and water), and [Cu(2)(OAc)(4)(OH(2))(2)] at room temperature and 10 K. The bond lengths and bridging O-C-O angles of the dimeric Cu(II) cage (Cu(2)O(10)C(8)) obtained from the multiple-scattering (MS) fitting of the X-ray absorption fine structure (XAFS) using a centrosymmetric model of [Cu(2)(Indo)(4)(DMF)(2)] gave Cu.Cu = 2.62(2) A, mean Cu-O(Ac) = 1.95(2) A, Cu-O(L) = 2.15(2) A, bridging O-C-O = 125(1) degrees, Cu displacement from plane 0.19 A compared with the XRD data Cu.Cu = 2.630(1) A, mean Cu-O(Ac) = 1.959 A, Cu-O(L) = 2.143(5) A, bridging O-C-O angles = 123.2(5) degrees, Cu displacement from plane 0.20 A. The excellent agreement between the XAFS- and XRD-derived data allowed the structures of related [Cu(2)(Indo)(4)L(2)] (L = DMA, NMP) complexes to be determined. All display a similar Cu(2)O(10)C(8) coordination geometry, which is independent of the nature of the axial ligand. While XAFS analysis of [Cu(2)(Indo)(4)(OH(2))(2)] and [Cu(2)(OAc)(4)(OH(2))(2)] indicates a coordination geometry similar to that of [Cu(2)(Indo)(4)L(2)] (L = DMF, DMA, NMP), removal of symmetry restraints in the MS model is required to obtain axial bond lengths comparable to those derived in the XRD structures of the acetate complex. For the Indo complex, the fitted bond lengths with the lower symmetry model give a mean Cu-L(OH2) bond distance within experimental errors of the value for [Cu(2)(Indo)(4)(DMSO)(2)] (2.16(2) A) (XRD). The difficulty in refining the Cu-O(OH2) distance of [Cu(2)(OAc)(4)(OH(2))(2)] and [Cu(2)(Indo)(4)(OH(2))(2)] using a centrosymmetric MS model is attributed to a symmetry reduction due to hydrogen-bonding effects characteristic of the aqua adducts, as is observed in the XRD structure of the acetate complex.     

Reactions of [Ru(H(2)O)(6)](2+) with water-soluble tertiary phosphines

In aqueous solutions under mild conditions, [Ru(H(2)O)(6)](2+) was reacted with various water-soluble tertiary phosphines. As determined by multinuclear NMR spectroscopy, reactions with the sulfonated arylphosphines L =mtppms, ptppms and mtppts yielded only the mono- and bisphosphine complexes, [Ru(H(2)O)(5)L](2+), cis-[Ru(H(2)O)(4)L(2)](2+), and trans-[Ru(H(2)O)(4)L(2)](2+) even in a high ligand excess. With the small aliphatic phosphine L = 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1(3,7)]decane (pta) at [L]:[Ru]= 12:1, the tris- and tetrakisphosphino species, [Ru(H(2)O)(3)(pta)(3)](2+), [Ru(H(2)O)(2)(pta)(4)](2+), [Ru(H(2)O)(OH)(pta)(4)](+), and [Ru(OH)(2)(pta)(4)] were also detected, albeit in minor quantities. These results have significance for the in situ preparation of Ru(II)-tertiary phosphine catalysts. The structures of the complexes trans-[Ru(H(2)O)(4)(ptaMe)(2)](tos)(4)x2H(2)O, trans-[Ru(H(2)O)(4)(ptaH)(2)](tos)(4)[middle dot]2H(2)O, and trans-mer-[RuI(2)(H(2)O)(ptaMe)(3)]I(3)x2H(2)O, containing protonated or methylated pta ligands (ptaH and ptaMe, respectively) were determined by single crystal X-ray diffraction.