Synthesis and crystal structure of uranium(IV) complexes with calix[n]arenes (n = 4, 6 and 8): mononuclear, polynuclear and 1D polymeric species

Reactions of UCl4 with calix[n]arenes (n = 4, 6) in THF gave the mononuclear [UCl2(calix[4]arene - 2H)(THF)2].2THF (.2THF) and the bis-dinuclear [U2Cl2(calix[6]arene - 6H)(THF)3]2.6THF (.6THF) complexes, respectively, while the mono-, di- and trinuclear compounds [Hpy]2[UCl3(calix[4]arene - 3H)].py (.py), [Hpy](4)[U2Cl6(calix[6]arene - 6H)].3py (.3py), [Hpy]3[U2Cl5(calix[6]arene - 6H)(py)].py (.py) and [Hpy]6[U3Cl11(calix[8]arene - 7H)].3py (.3py) were obtained by treatment of UCl4 with calix[n]arenes (n = 4, 6, 8) in pyridine. The sodium salt of calix[8]arene reacted with UCl4 to give the pentanuclear complex [U{U2Cl3(calix[8]arene - 7H)(py)5}2].8py (.8py). Reaction of U(acac)4 (acac = MeCOCHCOMe) with calix[4]arene in pyridine afforded the mononuclear complex [U(acac)2(calix[4]arene - 2H)].4py (.4py) and its treatment with the sodium salt of calix[8]arene led to the formation of the 1D polymer [U2(acac)6(calix[8]arene - 6H)(py)4Na4]n. The sandwich complex [Hpy]2[U(calix[4]arene - 3H)2][OTf].4py (.4py) was obtained by treatment of U(OTf)4 (OTf = OSO2CF3) with calix[4]arene in pyridine. All the complexes have been characterized by X-ray diffraction analysis.     

Cation and anion diversity in [M(dithiooxalate)2]2- salts: structure robustness in crystal synthesis

A series of crystalline salts based on the [M(dto)2]2- (dto = 1,2-dithiooxalate, M = Ni, Pt, Cu) dianion with hydrogen-bond donor cations have been synthesised following a molecular tectonics approach. The chelating M(dto)[dot dot dot]HN supramolecular synthon has been exploited in a systematic study of its robustness. The effects of competition between hydrogen-bond acceptors, of the shape and functionality of the cations and of varying the metal in the anion are discussed. The preparation and structural characterisation of the new crystalline phases [4,4'-H(2)bipy][Pt(dto)2] (2), [HNC5H4CO2H-4]2[Pt(dto)2] (5), [HNC5H4CO2H-3]2[Pt(dto)2] (6), [HNC5H4CH2CO2H-4]2[Ni(dto)2] (7), [HNC(5)H(4)CH(2)CO(2)H-3]2[Ni(dto)2] (8), [HNC5H4CONH2-4]2[Ni(dto)2] (9), [HNC5H4CHNOH-4]2[Ni(dto)2] (10), [HNC5H4CHNOH-3]2[Ni(dto)2] (11), [4,4'-H2bipip][Ni(dto)2] (12), [H2NC5H9CO2H-4]2[Pt(dto)2] (12), [H2NC5H9CO2H-4]2[Cu(dto)2] (14), [H2NC5H9CO2H-3]2[Ni(dto)2][H2O]2 (15), [H2NC5H9CO2H-3]2[Pt(dto)2][H2O]2 (16), [H2NC5H9CO2H-3]2[Cu(dto)2][H2O]2 (17), [H(Me)NC5H9CO2H-4]2[Ni(dto)2][H2O]2 (18) is reported. The charge-assisted NH[dot dot dot]dto synthon is formed in each of compounds 1-20, and is apparently much more robust than the conventional synthons used (such as the carboxylic acid dimer), which have a much lower rate of occurrence. The NH[dot dot dot]dto synthon may be generalised to 3- and 4-pyridinium species and 3- and 4-piperidinium derivatives. In the latter cases branching of the hydrogen-bond networks through the NH2 groups arises. The robustness of the NH...dto synthon allows structures of the form [NH cation]2[M(dto)2] to be regarded as being formed by the packing of neutral supermolecules. Cases of isomorphism (as in 16-18) and latent polymorphism (e.g. in 4 and 6) are noted.     

Influence of Molecular Structure on the Dimerization Reactivity of Germaaromatic Compounds： a Theoretical Study

Density functional theory (DFT) calculations, at the B3LYP/6-311G** level of theory, were performed to study the reaction mechanism and potential energy surface of the [2 + 2], [4 + 2] and [4 + 4] dimerization reactions of some germaaromatic compounds. The influence of reactant's molecular structure and benzene solvent on the potential energy surface of the studied reactions was investigated. Our calculation results show that [2 + 2] and [4 + 4] reactions are concerted and synchronous processes; while [4 + 2] reactions proceed via a concerted but asynchronous way in general. [2 + 2] and [4 + 2] reactions of germabenzenes and 1-germana- phthalene proceed much more easily than the corresponding [4 + 4] reaction, both thermo- dynamically and kinetically; while most [4 + 2] paths have lower activation barrier than the corres- ponding [2 + 2] ones. As the number of six-membered aromatic rings in reactant molecules becomes larger, [2 + 2], [4 + 2] and [4 + 4] reactions become easier to proceed. The influence of substituents at the Ge atom of germabenzenes on the potential energy surface of [2 + 2] and [4 + 2] reactions correlates with their electronic properties and volume. Solvent effect is not crucial for the potential energy surfaces of the studied reactions.     

NiTi过渡金属团簇的结构和芳香性的理论研究

在B3PW91/6-311+G(d)计算水平上, 计算并讨论了Ni₄Ti₂, [Ni₄Ti₂]²⁺, [Ni₄Ti₂]^2-与Ni₄Ti₄, [Ni₄Ti₄]²⁺, [Ni₄Ti₄]^2-团簇的几何结构和芳香性. 在构型优化过程中得到了Ni₄Ti₂(D_4h), [Ni₄Ti₂]²⁺(D_4h), [Ni₄Ti₂]^2-(D_4h)和Ni₄Ti₄(D_2h)4个稳定构型, 发现当引入上下2个Ti原子后, Ni₄环成为了平面正方形构型. 核无关化学位移(NICS)计算结果表明, Ni₄Ti₂(D_4h)与Ni₄Ti₄(D_2h)的NICS值为正, 而[Ni₄Ti₂]²⁺(D_4h)和[Ni₄Ti₂]^2-(D_4h)的NICS值为负, 且[Ni₄Ti₂]^2-(D_4h)的NICS值更负. 同时还发现, 由s与d轨道参与形成的反磁性环流是引起[Ni₄Ti₂]²⁺(D_4h)和[Ni₄Ti₂]^2-(D_4h)具有较大芳香性的主要原因; 其中Ti原子主要提供d_z²与s轨道, 而Ni原子主要利用其d_z²与d_x²-y²轨道形成正方形环, 它们之间构成了球状的d轨道环流, 且[Ni₄Ti₂]²⁺(D_4h)和[Ni₄Ti₂]^2-(D_4h)中还有非常明显的π轨道环流.     

Probing ruthenium-acetylide bonding interactions: synthesis, electrochemistry, and spectroscopic studies of acetylide-ruthenium complexes supported by tetradentate macrocyclic amine and diphosphine ligands

The synthesis and spectroscopic properties of trans-[RuL4(C[triple bond]CAr)2] (L4 = two 1,2-bis(dimethylphosphino)ethane, (dmpe)2; 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane, 16-TMC; 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane, N2O2) are described. Investigations into the effects of varying the [RuL4] core, acetylide ligands, and acetylide chain length for the [(-)C[triple bond]C(C6H4C[triple bond]C)(n-1)Ph] and [(-)C[triple bond]C(C6H4)(n-1)Ph] (n = 1-3) series upon the electronic and electrochemical characteristics of trans-[RuL4(C[triple bond]CAr)2](0/+) are presented. DFT and TD-DFT calculations have been performed on trans-[Ru(L')4(C[triple bond]CAr)2](0/+) (L' = PH3 and NH3) to examine the metal-acetylide pi-interaction and the nature of the associated electronic transition(s). It was observed that (1) the relationship between the transition energy and 1/n for trans-[Ru(dmpe)2{C[triple bond]C(C6H4C[triple bond]C)(n-1)Ph}2] (n = 1-3) is linear, and (2) the sum of the d(pi)(Ru(II)) --> pi*(C[triple bond]CAr) MLCT energy for trans-[Ru(16-TMC or N2O2)(C[triple bond]CAr)2] and the pi(C[triple bond]CAr) --> d(pi)(Ru(III)) LMCT energy for trans-[Ru(16-TMC or N2O2)(C[triple bond]CAr)2]+ corresponds to the intraligand pi pi* absorption energy for trans-[Ru(16-TMC or N2O2)(C[triple bond]CAr)2]. The crystal structure of trans-[Ru(dmpe)2{C[triple bond]C(C6H4C[triple bond]C)2Ph}2] shows that the two edges of the molecule are separated by 41.7 A. The electrochemical and spectroscopic properties of these complexes can be systematically tuned by modifying L4 and Ar to give E(1/2) values for oxidation of trans-[RuL4(C[triple bond]CAr)2] that span over 870 mV and lambda(max) values of trans-[RuL4(C[triple bond]CAr)2] that range from 19,230 to 31,750 cm(-1). The overall experimental findings suggest that the pi-back-bonding interaction in trans-[RuL4(C[triple bond]CAr)2] is weak and the [RuL4] moiety in these molecules may be considered to be playing a "dopant" role in a linear rigid pi-conjugated rod.     

Room-temperature phosphorescence and energy transfer in luminescent multinuclear platinum(II) complexes of branched alkynyls

A series of luminescent branched platinum(II) alkynyl complexes, [1,3,5-{RC[triple bond]C(PEt3)2PtC[triple bond]C-C6H4C[triple bond]C}3C6H3] (R=C6H5, C6H4OMe, C6H4Me, C6H4CF3, C5H4N, C6H4SAc, 1-napthyl (Np), 1-pyrenyl (Pyr), 1-anthryl-8-ethynyl (HC[triple bond]CAn)), [1,3-{PyrC[triple chemical bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}2-5-{(iPr)3SiC[triple bond]C}C6H3], and [1,3-{PyrC[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}2-5-(HC[triple bond]C)C6H3], was successfully synthesized by using the precursors [1,3,5-{Cl(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}3C6H3] or [1,3-{Cl(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}2-5-{(iPr)3SiC[triple bond]C}C6H3]. The X-ray crystal structures of [1,3,5-{MeOC6H4C[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}3C6H3] and [1,8-{Cl(PEt3)2PtC[triple bond]C}2An] have been determined. These complexes were found to show long-lived emission in both solution and solid-state phases at room temperature. The emission origin of the branched complexes [1,3,5-{RC[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}3C6H3] with R=C6H5, C6H4OMe, C6H4Me, C6H4CF3, C5H4N, and C6H4SAc was tentatively assigned to be derived from triplet states of predominantly intraligand (IL) character with some mixing of metal-to-ligand charge-transfer (MLCT) (dpi(Pt)-->pi*(C[triple bond]CR)) character, while the emission origin of the branched complexes with polyaromatic alkynyl ligands, [1,3,5-{RC[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}3C6H3] with R=Np, Pyr, or HC[triple bond]CAn, [1,3-{PyrC[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}2-5-{(iPr)3SiC[triple bond]C}C6H3], [1,3-{PyrC[triple bond]C(PEt3)2PtC[triple bond]CC6H4C[triple bond]C}2-5-(HC[triple bond]C)C6H3], and [1,8-{Cl(PEt3)2PtC[triple bond]C}2An], was tentatively assigned to be derived from the predominantly 3IL states of the respective polyaromatic alkynyl ligands, mixed with some 3MLCT (d(pi)(Pt)-->pi*(C[triple bond]CR)) character. By incorporating different alkynyl ligands into the periphery of these branched complexes, one could readily tune the nature of the lowest energy emissive state and the direction of the excitation energy transfer.     

Proton-induced cis-trans conversion of a platinum(II) center coordinated by L-cysteinatocobalt(III) metalloligands

Treatment of LambdaL-[Co(L-cys-N,S)(en)2]+ (l-H2cys = L-cysteine) with [PtCl4]2- in water, followed by the addition of acid, gave an S-bridged CoIII2PtII trinuclear complex ([1]4+), which was reversibly converted to its deprotonated complex ([2]2+) in an aqueous solution. While [1]4+ formed only a trans isomer, [2]2+ existed as a mixture of trans and cis isomers. The selective formation of a cis isomer was achieved by treatment of [1]4+ or [2]2+ with phthalic acid in water, which afforded a unique CoIII4PtII2 hexanuclear complex ([3]4+). Complex [3]4+ was reverted back to [1]4+ by treatment with aqueous HCl, accompanied by the complete cis-to-trans conversion.     

Hybrid molecular material exhibiting single-molecule magnet behavior and molecular conductivity

Two unique materials based on Mn4 single-molecule magnet (SMM) clusters (ST=9) and integer or non-integer average valent platinum maleonitriledithiolate (mnt2-) complexes, [{MnII2MnIII2(hmp)6(MeCN)2}{Pt(mnt)2}2][Pt(mnt)2]2.2MeCN (1) and [{MnII2MnIII2(hmp)6(MeCN)2}{Pt(mnt)2}4][Pt(mnt)2]2 (2), were synthesized by the material diffusion method and electrochemical oxidation, respectively (hmp-=2-hydroxymethylpyridinate). 1 and 2 are comprised of four and six [Pt(mnt)2]n- units, respectively, in addition to a common MnII2MnIII2 double-cuboidal unit, [MnII2MnIII2(hmp)6(MeCN)2]4+ (hereinafter [Mn4]4+). Among the [Pt(mnt)2]n- units, two units in 1 and four units in 2 are coordinated with the [Mn4]4+ unit, forming a 1D chain of {-[Mn4]-[Pt(mnt)2]2-} for 1 and a discrete subunit of {[Pt(mnt)2]2-[Mn4]-[Pt(mnt)2]2} for 2. The other two [Pt(mnt)2]n- units, occupying void space of the packing, form a stacking column with the coordinating [Pt(mnt)2]n- units, finally constructing hybrid frames of aggregates consisting of [Mn4]4+ units and [Pt(mnt)2]n- units. Electronic conductivity measurements revealed that 1 is an insulator and 2 is a semiconductor with sigma=0.22 S.cm(-1) at room temperature and an activation energy of 136 meV. Detailed magnetic measurements proved that the [Mn4]4+ units in 1 and 2 behave as SMMs with an ST=9 ground state at low temperatures. There is no significant interaction between [Mn4]4+ units and [Pt(mnt)2]n- units, but interactions between localized spins of [Pt(mnt)2]n- were detected even in 2 at low temperatures where the conductivity is electronically insulated. 2 is the first example of a hybridized material exhibiting SMM behavior and electronic conductivity.     

Further study of the reaction of Fe2+ with CN-: synthesis and characterization of cis and trans [FeII,III(CN)4L2]n- complexes

The reaction of Fe2+ with CN-, which was first performed in 1704, has been used to synthesize a new series of basic [FeII,III(CN)4L2]n- complexes, where L is a monodentate ligand. trans-Na2[FeII(CN)4(DMSO)2] and cis-[NEt4]2[FeII(CN)4(pyridine)2] are synthesized by the direct reaction of FeCl2 with 4 equiv of CN- in DMSO or pyridine. Air oxidation of the latter compound gives cis-[NEt4][FeIII(CN)4(pyridine)2]. The non-cyanide ligands in these complexes undergo facile ligand exchange reactions with solvent. Reaction of cis-[NEt4]2[FeII(CN)4(pyridine)2] with CO at room temperature gives trans-[NEt4]2[FeII(CN)4(pyridine)(CO)].     

Tetranuclear [Rh4(mu-PyS2)2(diolefin)4] complexes as building blocks for new inorganic architectures: synthesis of coordination polymers and heteropolynuclear complexes with electrophilic d8 and d10 metal fragments

The reaction of [Rh4(mu-PyS2)2(cod)4] (PyS2 = 2,6-pyridinedithiolate, cod = 1,5-cyclooctadiene) with CF3SO3Me gave the cationic complex [Rh(4)(mu-PyS(2)Me)(2)(cod)4][CF3SO3]2 (1) with two 6-(thiomethyl)pyridine-2-thiolate bridging ligands from the attack of Me+ at the terminal sulfur atoms of the starting material. Under identical conditions [Rh4(mu-PyS2)2(tfbb)4] (tfbb = tetrafluorobenzobarrelene) reacted with CF3SO3Me to give the mixed-ligand complex [Rh(4)(mu-PyS2)(mu-PyS2Me)(tfbb)4][CF3SO3] 2. The nucleophilicity of the bridging ligands in the complexes [Rh4(mu-PyS2)2(diolefin)4] was exploited to prepare heteropolynuclear species. Reactions with [Au(PPh3)(Me2CO)][ClO4] gave the hexanuclear complexes [(PPh3)2Au2Rh4(mu-PyS2)2(diolefin)4][ClO4]2 (diolefin = cod (3), tfbb (4)). The structure of 4, solved by X-ray diffraction methods, showed the coordination of the [Au(PPh3)]+ fragments to the peripheral sulfur atoms in [Rh4(mu-PyS2)2(diolefin)4] along with their interaction with the neighbor rhodium atoms. Neutral coordination polymers of formula [ClMRh4(mu-PyS2)2(diolefin)4]n (M = Cu (5, 6), Au (7)) result from the self-assembly of alternating [Rh4(mu-PyS2)2(diolefin)4] ([Rh4]) blocks and MCl linkers. The formation of the infinite polymetallic chains was found to be chiroselective for M = Cu; one particular chain contains exclusively homochiral [Rh4] complexes. Cationic heterometallic coordination polymers of formula [MRh4(mu-PyS2)2(diolefin)4]n[BF4]n (M = Ag (8, 9), Cu (10, 11)) and [Rh5(mu-PyS2)2(diolefin)5]n[BF4]n (12, 13) result from the reactions of [Rh4] with [Cu(CH2CN)4]BF4, AgBF4, and [Rh(diolefin)(Me2CO)2]BF4, respectively. The heterometallic coordination polymers exhibit a weak electric conductivity in the solid state in the range (1.2-2.8) x 10(-7) S cm(-1).     

A family of oxo-chalcogenide molybdenum and tungsten complexes, (n-Bu4N)2[M2O2(mu-Q)2(1,3-dithiole-2-thione-4,5-dithiolate)2] (M = Mo, W; Q = S, Se): new synthetic entries, structure, and gas-phase behavior

A new series of complexes with the general formula (n-Bu4N)2[M2O2(micro-Q)2(dmit)2] (where M = Mo, W; Q = S, Se; dmit = 1,3-dithiole-2-thione-4,5-dithiolate) have been prepared. Fragmentation of the trinuclear cluster (n-Bu4N)2[Mo3(micro3-S)(micro-S2)3(dmit)3] in the presence of triphenylphosphine (PPh3) gives the dinuclear compound (n-Bu4N)2[Mo2O2(micro-S)2(dmit)2] [(n-Bu4N)2[2]], which is formed via oxidation in air from the intermediate (n-Bu4N)2[Mo3(micro3-S)(micro-S)3(dmit)3] [(n-Bu4N)2[1]] complex. Ligand substitution of the molybdenum sulfur bridged [Mo2O2(micro-S)2(dimethylformamide)6]2+ dimer with the sodium salt of the dmit dithiolate also affords the dianionic compound (n-Bu4N)2[2]. The whole series, (n-Bu4N)2[Mo2O2(micro-Se)2(dmit)2] [(n-Bu4N)2[3]], (n-Bu4N)2[W2O2(micro-S)2(dmit)2] [(n-Bu4N)2[4]], (n-Bu4N)2[W2O2(micro-Se)2(dmit)2] [(n-Bu4N)2[5]], and (n-Bu4N)2[Mo2O2(micro-S)2(dmid)2] [(n-Bu4N)2[6]; dmid = 1,3-dithiole-2-one-4,5-dithiolate], has been synthesized by the excision of the polymeric (Mo3Q7Br4)x phases with PPh3 or 1,2-bis(diphenylphosphanyl)ethane in acetonitrile followed by the dithiolene incorporation and further degradation in air. Direct evidence of the presence of the intermediates with the formula [M3Q4(dmit)3]2- (M = Mo, W; Q = S, Se) has been obtained by electrospray ionization mass spectrometry. The crystal structures of (n-Bu4N)2[1], (PPh4)2[Mo2O2(micro-S)2(dmit)2] [(PPh4)2[2]; PPh4 = tetraphenylphosphonium], (n-Bu4N)2[2], (n-Bu4N)2[4], (PPh4)2[W2O2(micro-Se)2(dmit)2] [(PPh4)2[5]], and (n-Bu4N)2[6] have been determined. A detailed study of the gas-phase behavior for compounds (n-Bu4N)2[2-6] shows an identical fragmentation pathway for the whole family that consists of a partial breaking of the two dithiolene ligands followed by the dissociation of the dinuclear cluster.     

Syntheses and reactivity studies of solvated dirhenium acetonitrile complexes

Fully and partially solvated triply-bonded [Re2]4+ complexes have been synthesized and their X-ray structures are described. A fully solvated dirhenium salt with BArf [tetrakis(3,5-bis(trifluoromethyl)phenyl)borate] as the counter anion [Re2(CH3CN)10][BArf]4 () has been characterized. The solubility of the complex in CH2Cl2 and THF in addition to CH3CN offers the possibility of improved reactivity. The structure of [Re2(micro-O)(CH3CN)10][BF4]4 () that possesses a linear [Re(III)-O-Re(III)]4+ unit is reported. Protonation reactions of cis-Re2Cl2(dppm)2(O2CCH3)2 and trans-Re2Cl4(dppm)2 with HBF4.Et2O in acetonitrile afforded cis and trans [Re2(dppm)2(CH3CN)6][BF4]4 ( and ), respectively. Prolonging the reaction time, however, does not lead to fully solvated complex [Re2(CH3CN)10][BF4]4. The neutral nitrogen donor ligands pynp (2-(2-pyridyl)-1,8-naphthyridine) and tznp (2-(2-thiazolyl)-1,8-naphthyridine) react readily with [Re2(CH3CN)10][BF4]4 to provide trans-[Re2(pynp)2(CH3CN)4][BF4]4 and trans-[Re2(tznp)2(CH3CN)4][BF4]4. The X-ray structures trans-[Re2(pynp)2(CH3CN)4][BF4]4 () and trans-[Re2(tznp)2(CH3CN)4][BF4]3[PF6] () have been determined.     

两种异马来二氰基二硫烯镍(II)-取代苄基喹啉鎓盐的制备及其光谱性质和晶体结构

以甲醇为溶剂,将异马来二氰基二硫烯酸钾[K2(i-mnt)]和六水氯化镍分别与溴化4-溴苄基喹啉盐([4-BrBzQl]Br)或溴化4-硝基苄基喹啉盐([4-NO2BzQl]Br)直接反应,得到两种新的离子对配合物[4-BrBzQl]2[Ni(i-mnt)2](1)和[4-NO2BzQl]2[Ni(i-mnt)2](2);测定了其红外光谱和紫外-可见光谱,并利用X射线衍射表征了配合物1的晶体结构.结果表明,配合物[4-BrBzQl]2[Ni(i-mnt)2]为三斜晶系,P-1空间群,其每个不对称单元含半个[Ni(i-mnt)2]2-阴离子和1个[4-BrBzQl]+阳离子,晶体中的阴、阳离子通过静电作用和C-H…S、C-H…N氢键作用形成网络结构.     

Synthesis and luminescence behaviour of novel heterodecanuclear silver(I)-rhenium(I) alkynyl complexes. X-ray crystal structures of [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Me2bpy)(CO)3]4](PF6)2 and [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Br2phen)(CO)3]4](PF6)2

A novel series of luminescent heterodecanuclear mixed-metal alkynyl complexes, [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(N--N)(CO)3]4](PF6)2, (N--N = tBu2bpy, Me2bpy, phen, Br2phen), have been successfully synthesized; the X-ray crystal structures of [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Me2bpy)(CO)3]4](PF6)2 and [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Br2phen)(CO)3]4](PF6)2 have also been determined.     

The first, discrete Zn4 tetrahedron with a selenium atom in the center: x-ray structure and solution study of [Zn4(mu4-Se)[Se2P(OPr)2]6

The first discrete, selenium-centered tetranuclear zinc cluster [Zn4(mu4-Se)[Se2P(OPr)2]6] was isolated and characterized. The cluster consists of six edge-bridged dsep ligands with four zinc atoms in a slightly distorted tetrahedron and a mu4-Se atom in the center. In addition, 12 mu2-bridging selenium atoms form a Se12 icosahedron. From variable-temperature 31P NMR studies, it was observed that the cluster [Zn4(Se)[Se2P(OPr)2]6] is partly decomposed to [Zn[Se2P(OPr)2]2] and the monomeric species [Zn[Se2P(OPr)2]2] is further in equilibrium with its dimer [Zn[Se2P(OPr)2]2]2.     

Alpha-amino acids with metallocenyl side chains

A straightforward method for the synthesis of enantiomerically pure bis(valine)metallocenes is presented. Derivatives of lithium cyclopentadienylvaline 1a, b were obtained by addition of the (R)- or (S)-Sch?llkopf reagents to 6,6-dimethylfulvene as single enantiomers and gave with FeCl2 or [RuCl2(dmso)4] the chiral metallocenes [Fe[C5H4-CMe2-[C4H2N2(OMe)2iPr]]2] (2a, b) and [Ru[C5H4-CMe2-[C4H2N2(OMe)2iPr]]2] (3a, b). Complex 2b was hydrolyzed to the ferrocenylene-bis(valine-methylester) [[Fe[C5H4-CMe2-CH(NH3+)COOMe]2]2+(Cl-)2] (7) without racemization. Complex 7 could be used as ligand and was treated with [[Cp*IrCl2]2] to afford [Fe[C5H4-CMe2-CH(COOMe)(NH2-IrCp*Cl2)]2] (10). The reactions of 1 with CoCl2, [Re(CO)5Br], [[(cod)RhCl2]2] (cod= 1,5-cyclooctadiene) or [Cp*MCl3] (M= Ti, Zr) gave the cyclopentadienyl complexes [[Co[C5H4-CMe2-[C4H2N2(OMe)2iPr]]2]+ I-] (11) and [Re[C5H4-CMe2-[C4H2N2(OMe)2iPr]](CO)3] (13), [(C8H12)Rh[C5H4-CMe2-[C4H2N2(OMe)2(iPr)]]] (14). [[Rh[C5H4-CMe2-[C4H2N2(OMe)2(iPr)]]I]2(mu-I)2] (15), [Cp*Cl2Ti-[C5H4-CMe2-[C4H2N2(OMe)2(iPr)]]] (16), and [Cp*Cl2Zr[C5H4-CMe2-[C4H2N2(OMe)2(iPr)]]] (17), with chiral valine derivatives as substituents on the cyclopentadienyl ring and with excellent diastereoselectivities. Also the Seebach reagent (Boc-BMI) or O'Donnell reagent could be added to 6,6-dimethylfulvene to give the lithium cyclopentadienides Li[C5H4-CMe2-[C3H2(tBu)(N-Boc)(NMe)O]] (18) and Li[C5H4-CMe2-CH(NCPh2)(COOEt)] (21), which formed the ferrocene derivatives [Fe[C5H4-CMe2-[C3H2(tBu)(N-Boc)(NMe)O]]2] (19) and [Fe[C5H4-CMe2-CH(NCPh2)(COOEt)]2] (22). The stable cobaltocinium cation in 11 and the complex 19 could be hydrolyzed to the metallocenes 12 and [Fe(C5H4-CMe2-CH(NH3+)(COO-)]2] (20) with two valines in the 1,1'-position. The structures of 2a, b, 11, 15, and 16 were determined by X-ray diffraction and confirm the diastereomeric purity of the compounds.     

Novel network polymers based on calixresorcinarenes

The novel network polymers 2a-2d based on calix[4]resorcinarene derivatives were obtained with yields 2a: 80%, 2b: 90%, 2c: 70%, 2d: 70%. Polymers 2a and 2b containing fragments of tetramethylcalix[4]resorcinarene or tetraphenylcalix[4]resorcinarene as a repeating units were synthesized by condensation cis-tetramethylcalix[4]resorcinarene or cis-tetraphenylcalix[4]resorcinarene with formaldehyde. Polymers 2c and 2d containing fragments of furylcalix[4]resorcinarene were obtained by condensation of formaldehyde with products of calix[4]resorcinarene and furfural interaction. The IR spectra and sorption properties of the polymers were researched. It is found out that 2a-2d can participate in the cation-exchange reaction.     

A NOVEL SYNTHESIS OF 2-SUBSTITUTED-4H-THIENO [2,3-d][1,3] OXAZIN-4-ONE AND 2,3-DISUBSTITUTED THIENO [2,3-d]PYRIMIDIN-4(3H)-ONE DERIVATIVES

Abstract

The synthesis of acetic 2-{[1-methyl-2-(4-oxo-5,6,7,8-tetrahydro-4H-benzo [4,5]-thieno [2,3-d] [1,3-oxazin-2-yl)ethylidene]amino}-4,5,6,7-tetrahydrohenzo[b]thiophene ?3-carboxylic acid anhydride 5 and 2-(oxopropyl)-5,6,7,8-tetrahydro-4H-benzo-[4,5] thieno[2,3-d][1,3]oxazin-4-one 7, has been achieved in three steps from ethyl 2-amino-4,5,6,7-tetrahydrobenzo(b]thiophene-3-carboxlate 1 via the reaction with ethyl acetoacetate followed by hydrolysis and acetic anhydride-induced cyclization. The 2-substituent in compound 5 has two functional groups i.e. active methylene and acid anhydride which are suitably located for intramolecular transformation. Thermal and/or base catalyzed intramolecular cyclization of 5 afforded 2-(4-acetoxy-(hydroxyl)-2-methyl-5,6,7,8-tetrahydrobenzo[4,5] thieno[2,3-b]pyridin-3-yl)-5,6,7,8- tetrahydro-4H-benzo[4,5]thieno[2,3-d] [1,3]oxazin-4-one 10 and 9 respectively. Treatment of 5 with hydrazine hydrate, aromatic and/or heterocyclic amines induced the same intramolecular cyclization with a concomitant oxazine-pyrimidine interconversion to give 3-amino(aryl or heteryl)-2-(4-hydroxy-5,6,7,8-tetrdhydrobenzo-[4,5]thieno[2,3-b]pyridin-3-yl)-3,4,5,6,7,8-hexahydrobenzo[4,5] thieno[2,3-d] pyrimid in-4-one 11–14 respectively.     

Transition metal-catalyzed [4 + 2 + 2] cycloadditions of bicyclo[2.2.1]hepta-2,5-dienes (norbornadienes) and bicyclo[2.2.2]octa-2,5-dienes

The transition-metal-catalyzed [4 + 2 + 2] cycloadditions of norbornadienes, bicyclo[2.2.2]octa-2,5-diene, and benzobarrelene with 1,3-butadienes proceed in excellent yields using cobalt-based catalytic systems. Two key distinctions between these [4 + 2 + 2] cycloadditions and the corresponding transition-metal-catalyzed [2 + 2 +2] reactions of norbornadiene are the requirement of a bimetal catalytic system with a bisphosphine ligand for the former and exclusive regioselectivity in the [4 + 2 + 2] reaction of 2-substituted norbornadienes to produce 1-substituted adducts. These distinctions may indicate two distinct mechanisms for the [4 + 2 + 2] and [2 + 2 + 2] reactions.     

Facile Regioselective Synthesis of Pyrano[3,2-c][1]benzo-thiapyran-5(2H)-one and 2-Methyl Furo[3,2-c][1] Benzothiapyran-4-one

The hitherto unreported title compounds were obtained in good yields by the application of [3,3]sigmatropic rearrangement on 4-]2′-propynyloxy] [1]benzothiapyran-2-one and 4-[2′-propenyloxy][1]benzothiapyran-2-one or 4-[2′-chloro-2′-propenyloxy][1]benzothiapyran-2-one respectively.