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Improving thermostability of an enzyme can accelerate the relevant chemical reaction. Thus, the analysis and prediction of thermophilic proteins are conducive to protein engineering and enzyme design. In this study, a novel method based on two-step discrimination was proposed to distinguish between thermophilic and non-thermophilic proteins. The model was rigorously benchmarked on an objective dataset including 915 thermophilic proteins and 793 non-thermophilic proteins. Results showed that the overall accuracy of our method is 94.44% in 5-fold cross-validation, which is higher than those of other published methods. We believe that the two-step discriminated strategy will become a promising method in the relevant field of protein bioinformatics. [ABSTRACT FROM AUTHOR]

Palladium and CO.: The title reaction proceeds in the presence of CO, thus providing a synthesis for 1,3‐oxazin‐6‐ones (see scheme; DABCO=1,4‐diazabicyclo[2.2.2]octane, DMF=N,N‐dimethylformamide). The reaction tolerates a variety of functional groups on both the aryl ring and the amide of the substrate. Initial mechanistic studies suggest the activation of the alkenyl CH bond to be a key step. [ABSTRACT FROM AUTHOR]

A novel Cu(TFA)2-catalyzed oxidative tandem cyclization/1,2-alkyl migration of readily available enamino amides for the synthesis of pyrrolin-4-ones has been developed. The reaction tolerates a wide range of functional groups and is a reliable method for the rapid synthesis of substituted pyrrolin-4-ones in high yields under mild conditions. [ABSTRACT FROM AUTHOR]

Solvothermal reactions of Cu2(OH)2CO3 with 1,3-bis(pyridin-4-yl)propane (bpp) in the presence of aqueous ammonia in 4-iodotoluene/CH3CN or 1,4-diiodobenzene/CH3CN afforded two [Cu2I2]-based coordination polymers, namely catena-poly[[[di-μ-iodido-dicopper(I)]-bis[μ-1,3-bis(pyridin-4-yl)propane-κ2 N: N′]] p-toluidine tetrasolvate], {[Cu2I2(C13H14N2)2]·4C7H9N} n, (I), and the analogous 1,4-diiodobenzene monosolvate, {[Cu2I2(C13H14N2)2]·C6H4I2} n, (II). The [Cu2I2] unit of (I) lies on a centre of symmetry at the mid-point of the two I atoms, while that of (II) has a twofold axis running through the I...I line. In (I) and (II), each Cu centre is tetrahedrally coordinated by two μ-I and two N atoms from two different bpp ligands. Each rhomboid [Cu2I2] unit can be considered as a four-connecting node linked to the symmetry-related [Cu2I2] units via two pairs of bpp ligands to form a one-dimensional double chain along the c axis. The dimensions of the [Cu2I2(bpp)2]2 rings in (I) and (II) are different, which may be due to the presence of different guest solvent molecules in the structures. In (I), one p-toluidine molecule, derived from an Ullmann coupling reaction of 4-iodotoluene with ammonia, interacts with the [Cu2I2] cluster fragment through N-H...I hydrogen bonds, while the two p-toluidine molecules interact via N-H...N hydrogen bonds. In (II), two I atoms of each 1,4-diiodobenzene molecule are linked to the I atoms of the [Cu2I2] fragments from a neighbouring chain via I...I secondary interactions. [ABSTRACT FROM AUTHOR]

Abstract: Reactions of PdCl2·2H2O with 2equiv. of 4-(trimethylammonio)benzenethiolate (Tab) (prepared in situ from a mixture of TabHPF6 and Et3N in MeOH) and seven phosphine ligands: PPh3, 1,1-bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda), and 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda), afforded a family of mononuclear and dinuclear Pd(II)/Tab/phosphine complexes, [Pd2(PPh3)2(Tab)2(μ-Tab)2](PF6)4 (1), [Pd2(dppm)2(Tab)2(μ-Tab)](PF6)4 (2), [Pd2(dppb)(Tab)2(μ-Tab)2]Cl4 (3), [PdL(Tab)2](PF6)2 (4: L=dppe; 5: L=dppp) and {[PdL(Tab)2]2}Cl4 (6: L=dppeda; 7: L=dpppda). These compounds were characterized by elemental analysis, IR spectra, UV–Vis spectra, 1H and 31P{1H} NMR, electrospray ionization (ESI) mass spectra and single-crystal X-ray diffraction. In the structure of 1–7, each Pd(II) adopt an approximate square planar coordination geometry. The results provide an interesting insight into the chemistry of palladium(II)/thiolate/phosphine complexes. [Copyright &y& Elsevier]

Abstract: Reaction of silver nitrate with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in the presence of aminothiocarbamide in CH2Cl2/MeOH afforded an unexpected and low-yield binuclear complex [Ag2(dppatc)2](NO3)2·2MeOH (dppatc=N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) (1). An X-ray analysis revealed that the [Ag2(dppatc)2]2+ dication of 1 contains a centrosymmetric double half-open cage structure in which two Ag centers are bridged by a pair of the heteroscopionate dppatc ligands via four Ag-μ-S and four AgThe in situ-formed dppatc ligand in 1 could be readily generated by one-pot and high-yield reaction of diphenylphosphine with formaldehyde and aminothiocarbamide. Further reaction of AgNO3 with dppatc could produce 1 in a relatively high yield. The results provided an efficient route to the synthesis of dppatc and also an interesting insight into its coordination chemistry. [Copyright &y& Elsevier]

Reactions of a gold(i) thiolate complex [Au(Tab)2]2(PF6)2(Tab = 4-(trimethylammonio)benzenethiolate) with equimolar 1,2-bis(diphenylphosphine)ethane (dppe), 1,3-bis-(diphenylphosphine)propane (dppp) or 1,4-bis-(diphenylphosphine)butane (dppb) in MeOH–DMF–CH2Cl2gave rise to three polymeric complexes [Au2(Tab)2(dppe)]2(PF6)4·2MeOH (1·2MeOH), [Au2(Tab)2(dppp)]Cl2·0.5MeOH·4H2O (2·0.5MeOH·4H2O), and [Au4(μ-Tab)2(Tab)2(dppb)](PF6)4·4DMF (3·4DMF), respectively. Analogous reaction of 1with dppb in DMF/C2H4Cl2produced one tetranuclear complex [Au2(μ-Tab)(Tab)2]2Cl4·2DMF·4H2O (4·2DMF·4H2O). Complexes 1–4were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H and 31P{1H} NMR and single crystal X-ray analysis. Compounds 1and 2consist of [Au(Tab)]2dimeric fragments that are bridged by dppe or dppp ligands to form a 1D linear chain extending along the aaxis. For 3, each [Au4(Tab)2(μ-Tab)2] fragment is linked by a pair of dppb ligands to afford another 1D chain extending along the caxis. For 4, the four [Au(Tab)]+fragments are linked by two Au–Au bonds and two doubly bridging Tab ligands to form a {[Au(Tab)]4(μ-Tab)2} chair-like cyclohexane structure. Hydrogen-bonding interactions in 2and 4lead to the formation of interesting 2D hydrogen-bonded networks. The luminescent properties of 1–4in solid state were also investigated. [ABSTRACT FROM AUTHOR]

Four 1,3-benzenedicarboxylic acid derivatives, with substituted R (OH, COOH, NO2, Me) groups at the 5-position, were employed to explore their effect on the construction of supramolecular assemblies. Four coordination polymers, [Zn(OH2)(5-HO-1,3-BDC)(1,4-bpeb)]n(1), [Zn(1,3,5-HBTC)(1,4-bpeb)]n(2), {[Zn(5-NO2-1,3-BDC)(1,4-bpeb)]·2(H2O)0.5}n(3), and [Zn(5-Me-1,3-BDC)(1,4-bpeb)]n(4) (1,4-bpeb = 1,4-bis[2-(4-pyridyl)ethenyl]benzene, 5-HO-1,3-BDC = 5-hydroxy-1,3-benzenedicarboxylate, 1,3,5-H3BTC = 1,3,5-benzenetricarboxylate, 5-NO2-1,3-BDC = 5-nitro-1,3-benzenedicarboxylate, 5-Me-1,3-BDC = 5-methyl-1,3-benzenedicarboxylate) were prepared by the hydrothermal reactions of Zn(NO3)2·6H2O with 1,4-bpeb and 5-HO-1,3-H2BDC, 1,3,5-H3BTC, 5-NO2-1,3-H2BDC or 5-Me-1,3-H2BDC. All these compounds were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of 1has a 3D H-bonded structure derived from linking 1D comb-like [Zn(OH2)(5-HO-1,3-BDC)(1,4-bpeb)]nchains viaintermolecular H-bonding interactions between the coordinated H2O molecule and 1,4-bpeb or one COO−group and between the OH group and the other COO−group. 2has a 3D H-bonded net based on holding 2D [{Zn2(1,3,5-HBTC)2}4]nlayers through intermolecular H-bonding interactions between 1,4-bpeb and the uncoordinated COOH group. 3could be considered as a 6-fold interpenetrating 3D H-bonded supramolecular framework constructed by linking 2D [Zn4(5-NO2-1,3-BDC)4(1,4-bpeb)4]nnetworks through intermolecular H-bonding interactions between the water solvent molecules and the NO2group. 4has a 3-fold interpenetrating 3D framework in which each 2D (4,4) [Zn4(5-Me-1,3-BDC)4(1,4-bpeb)4]nnetwork is interpenetrated by two other equivalent nets. The Schläfli symbols for the four supramolecular frameworks are 41263, (4·62)2(426687), (63)(658) and 4462, respectively. The thermal stability and photoluminescent properties of 1–4were also investigated. [ABSTRACT FROM AUTHOR]

Abstract: Treatment of a suspension of AgNO3 and AgCl in MeOH with a solution of N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda) in CHCl3 afforded a binuclear complex [Ag2(dppeda)Cl](NO3)·2MeOH (1). The analogous reactions using AgSCN and dppeda in EtOH/CH2Cl2 gave rise to a polymeric complex [Ag2(dppeda)(SCN)2] n (2). Both compounds were fully characterized by elemental analyses, IR spectra, 1H(31P) NMR, and single-crystal X-ray crystallography. The cation of 1 shows an interesting molecular basket framework in which dppeda adopts a side-by-side coordination mode. Compound 2 possesses an unique 2D (6,3) layer network with 34-membered metallomacrocycles in which dppeda takes a end-to-end coordination mode. The 2D topological framework of 2 is rare in the chemistry of tetraphosphines. The photoluminescent properties of 1 and 2 in solid state at ambient temperature were investigated. [Copyright &y& Elsevier]

Reactions of trans-[(η5-C5Me5)2Mo2S2(μ-S)2] (1) with 2 equiv. of [Cu(MeCN)4]X (X = PF6−, ClO4−) produced two acetonitrile-coordinated cubane-like cationic clusters [(η5-C5Me5)2Mo2(μ3-S)4Cu2(MeCN)2]X2(X = PF6−(2), ClO4−(3)). Treatment of 2or 3with 4,4′-bipyridine (4,4′-bipy) or trans-1,2-bis(4-pyridyl)ethylene) (bpee) afforded two polymeric clusters {[(η5-C5Me5)2Mo2(μ3-S)4Cu2(L)]X2}n(4: L = 4,4′-bipy, X = PF6−; 5: L = bpee, X = ClO4−), while analogous reactions of 2or 3with 1,2-bis(4-pyridyl)ethane (bpea), 1,2-bis(diphenylphosphine)ethane (dppe), or 1,4-bis-(diphenylphosphine)butane) (dppb) formed three dimeric clusters [(η5-C5Me5)2Mo2(μ3-S)4Cu2(L)]2X4(6: L = bpea; X = PF6−; 7: L = dppe, X = ClO4−; 8: L = dppb, X = ClO4−). Clusters 2–8consist of a cubane-like [(η5-C5Me5)2Mo2(μ3-S)4Cu2] core with each Cu being coordinated by one labile MeCN molecule (2, 3) or by bridging dipyridyl or diphosphino ligands (4–8). 4or 5has a 1D zigzag chain structure while 6–8contain cyclic dimeric structures. The third-order non-linear optical (NLO) properties of 2–8in MeCN were investigated by Z-scan technique at 532 nm. These compounds showed strong third-order NLO absorption effects and self-defocusing properties, and their NLO performances were remarkably enhanced relative to those of 1. [ABSTRACT FROM AUTHOR]

Abstract: Reactions of CuX (X=CN, NCS) with bis(3,5-dimethylpyrazolyl)methane (dmpzm) gave rise to two new coordination polymers [CuX(dmpzm)] n (X=CN (2), NCS (3)). Compounds 2 and 3 were characterized by elemental analysis, IR spectra and X-ray crystallography. The molecular structure of 2 has a one-dimensional zigzag chain of [CuCN(dmpzm)] units while that of 3 consists of a one-dimensional single-strand spiral chain of [CuNCS(dmpzm)] units. The luminescence properties of CuX (X=I (1), CN (2), NCS (3)) adducts of dmpzm along with free dmpzm were also investigated. [Copyright &y& Elsevier]

A novel and efficient method for the oxidation of 2-arylindoles to synthesize 2-arylbenzoxazinones utilizing oxone as the sole oxidant has been developed. The reaction tolerates a wide range of functional groups and allows quick and atom-economical assembly of a variety of valuable 2-arylbenzoxazinones in high yields. [ABSTRACT FROM AUTHOR]

The use of the Cu-calixarene complex (CAL) in combination with TEMPO allows a high yielding oxidation of benzylic alcohols to the corresponding aldehydes with hydrogen peroxide as the oxidant. [ABSTRACT FROM AUTHOR]

The reactions of phosphonium salts, arylglyoxals, amines, and isocyanides give dihydrobenzazepinones in good yields via a sequential Ugi condensation and intramolecular Wittig reaction. [ABSTRACT FROM AUTHOR]

Treatment of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate)with [Cu(MeCN)4]PF6and NH4PF6(molar ratio= 1:2:1) in excess pyridine (py) produced one discrete trinuclearcluster [Et4N][Tp*WS3Cu2(py)3](PF6)2(2). Reactionsof 1with [Cu(MeCN)4]PF6, NH4PF6, and 4,4′-bipyridine (4,4′-bipy)(or 1,2-bis(4-pyridyl)ethane (bpea)) (molar ratio = 1:2:1:2) affordeda two-dimensional (2D) [Tp*WS3Cu2]-based cationicpolymer {[Tp*WS3Cu2(4,4′-bipy)1.5](PF6)·2MeCN}n(3·2MeCN) and a one-dimensional (1D) [Tp*WS3Cu2]-based cationic polymer {[(Tp*WS3Cu2)2(bpea)3](PF6)2·2DMF}n(4·2DMF),respectively. Analogous reactions of 1with CuCN, NH4PF6, and 4,4′-bipy (or 1,2-bis(4-pyridyl)ethylene(bpee)) (molar ratio = 1:2:1:2) gave rise to a 2D [Tp*WS3Cu2]-based polymer {[Tp*WS3Cu2(μ-CN)(4,4′-bipy)0.5]·MeCN}n(5·MeCN) and a three-dimensional (3D) [Tp*WS3Cu2]-based anionic polymer {[Et4N][(Tp*WS3Cu2)2{Cu(μ-CN)2.5}2(bpee)]·3MeCN}n(6·3MeCN), respectively. Compounds 2–6were characterized by elemental analysis, IR, UV–vis, 1H NMR, and single-crystal X-ray diffraction. The cluster cationof 2has a butterfly-shaped [Tp*WS3Cu2] core structure in which one [Tp*WS3] unit bindstwo Cu atoms via one μ3-S and two μ-S atoms. 3consists of one 2D (6,3) network in which butterfly-shaped[Tp*WS3Cu2] units are interlinked by the 4,4′-bipyligands. 4contains butterfly-shaped [Tp*WS3Cu2] units that are interconnected by bpea bridges toform one 1D zigzag chain. 5holds another 2D (6,3) networkin which the 1D [{Tp*WS3Cu2}2(μ-CN)2]nchains are bridged by 4,4′-bipyligands. 6possesses a 3-connected 3D (103) anionic net in which each 2D [{(Tp*WS3Cu2)2Cu2(μ-CN)4}4(μ-CN)4(bpee)2]n4n–network is interlinked to its neighboringones via pairs of bpee ligands. The isolation of 2–6with unstable [Tp*WS3Cu2] cores maybe ascribed to the coordination of N-donor ligands or linkers at Cu(I)centers of these cores and the formation of polydimensional [Tp*WS3Cu2]-based frameworks (in the case of 3–5). The third-order nonlinear optical (NLO)properties of 2–6in DMF were alsoinvestigated by using a femtosecond degenerate four-wave mixing (DFWM)technique at 800 nm. [ABSTRACT FROM AUTHOR]

New strategies for the oxidative cycloaddition of enones with enamines are developed. These cycloaddition reactions directly afford substituted aromatic amines, which are important in organic chemistry, in moderate to good yield. Cu(OAc)2/TFA is shown to be essential to achieve high reaction efficiency. [ABSTRACT FROM AUTHOR]

Abstract: In the absence of any additional ligands, the efficient N-arylation of nitrogen-containing heterocycles with aryl iodides catalyzed by relative low catalyst amount of Cu(OAc)2·H2O was developed. This simple catalytic system is involved in the C–N cross-coupling reaction and works for a variety of pyrazole, pyrrole, imidazole, triazole, indole, benzoimidazole, benzotriazole, carbazole, and anilines as well as aryl iodides with different electronic properties. Highly efficient copper(II)-catalyzed N-arylation protocol was established. [Copyright &y& Elsevier]

Abstract: Reactions of 25,26,27,28-tetrahydroxy-calix[4]arene (1) with 4 equiv. of m-carboxybenzenediazonium chloride in the presence of NaOAc∙3H2O in DMF produced a new azo calix[4]arene [H4L] (2) (H4L=5,11,17,23-tetrakis[(m-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]arene) in 96% yield. Hydrothermal reactions of Cd(NO3)2·4H2O with H4L at 90°C under pH=5.0–6.0 gave rise to a coordination polymer {[H3O]2[Cd7L4(DMF)4(EtOH)2(H2O)2]·5DMF·11.5EtOH·H2O}n (3). Compound 3 was characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Compound 3 consists of a 3D framework with an unprecedented (3346526371)(364135861) topology. The thermal properties of 2 and 3 were also investigated. [Copyright &y& Elsevier]

Abstract: Solvothermal reactions of CdSO4·8/3H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) and HCl in H2O, MeOH or EtOH afforded three coordination complexes [Cd5Cl2(μ-Cl)4(μ3-Cl)2(η,η,η-μ3-SO4)2(H2O)2(Htitmb)2] n (1), [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2(MeOH)2(titmb)2] n (2) and [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2] (3), respectively. All the compounds were characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 has a 1D chain in which each centrosymmetric double butterfly-shaped [Cd5Cl2(μ-Cl)4(μ3-Cl)2(H2O)2] unit interlinks with its equivalent ones via two couples of η,η,η-μ3-SO4 anions and two pairs of the Htitmb ligands. Compound 2 consists of one centrosymmetric [Cd5Cl2(μ-Cl)2(η,η,η-μ3-SO4)2(MeOH)4(titmb)2] unit that interconnects with equivalent ones via sharing Cd3 and its symmetry-related ones, forming a 1D zigzag chain. Compound 3 consists of a [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2] unit linked by a pair of titmb ligands. The results may provide some insight into solvent effects on the formation of different coordination compounds from the same components. [Copyright &y& Elsevier]

With N-acetyl aniline, N,N-dimethylaniline and aniline no reaction occurs. [ABSTRACT FROM AUTHOR]

Reactions of NiCl2·6H2O or Ni(ClO4)2·6H2O with 2,2′-bipyridine (2,2′-bipy), or 2-bis(diphenylphosphino)ethane (dppe) or 1,4-bis(diphenylphosphino)butane (dppb) followed by addition of [Zn(Tab)4](PF6)2 (1) resulted in the formation of one trinuclear cationic complex [(2,2′-bipy)4Ni3(μ-Tab)4]Cl0.5(PF6)5.5 (2), one mononuclear cationic complex [Ni(Tab)2(dppe)](PF6)2 (3), and one dinuclear cationic complex [Ni2(dppb)(μ-Tab)2(Tab)2](PF6)2(ClO4)2 (4). Complexes 2-4 were characterized by elemental analysis, IR, UV-vis, 1H and 31P NMR, and single-crystal X-ray diffraction. In the [(2,2′-bipy)4Ni3(μ-Tab)4]6+ hexacation of 2, the central Ni(II) atom is connected to two [Ni(2,2′-bipy)2]2+ fragments by two pairs of μ-Tab ligands, forming a linear trinuclear cationic structure. The Ni(II) center of the dication of 3 is tetrahedrally coordinated by two S atoms from two Tab ligands and two P atoms of one dppe ligand. Complex 4 has a dimeric cationic structure in which two [(Tab)Ni]2+ species are linked by a pair of μ-Tab ligands and one dppb ligand. Complexes 2-4 displayed high catalytic activity toward the cross-coupling reactions of arylboronic acids and amines to produce N-arylated amines. [ABSTRACT FROM AUTHOR]

Abstract: Reactions of Zn(NO3)2∙6H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) in the presence of 1,4-benzenedicarboxylic acid (1,4-H2BDC) or 1,3-benzenedicarboxylic acid (1,3-H2BDC) under hydrothermal conditions afforded one 1D and one 2D coordination polymers [Zn3(titmb)2(1,4-BDC)3(H2O)6] (1) and [Zn2(titmb)(1,3-BDC)2(H2O)] (2), respectively. Similar reactions of Zn(NO3)2∙6H2O with 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bitmb) and 1,4-H2BDC gave rise to one 2D coordination polymer [Zn2(bitmb)2(1,4-BDC)2] (3). Compound 1 has a 1D linear chain formed from linking 24-membered [Zn2(titmb)2] metallamacrocycles and [Zn(1,4-BDC)(H2O)2] units via imidazolyl groups of titmb ligands. Compound 2 has a 2D network assembled from connecting spiral [Zn n (1,3-BDC) n ] chains with titmb linkers, while compound 3 also has a 2D network formed by linking 24-membered [Zn2(bitmb)2] metallamacrocycles via 1,3-BDC bridges. The ligands titmb and bitmb in compounds 1–3 adopt less-common cis–trans–trans and cis–trans conformations, respectively. Their thermal and photoluminescent properties were also investigated. [Copyright &y& Elsevier]

Hydrothermal reactions of CdSO4 with tetrakis(4-pyridyl)cyclobutane (tpcb) and 1,3-benzenedicarboxylic acid (1,3-H2BDC) or 5-nitro-1,3-benzenedicarboxylic acid (5-NO2-1,3-H2BDC) resulted in the formation of two coordination polymers [Cd(tpcb)0.5(1,3-BDC)]n (1) and {[Cd2(tpcb)(5-NO2-1,3-BDC)2(OH2)2]·4H2O}n (2), respectively. Compounds 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. 1 and 2 exhibit two different types of two-fold interpenetrating 3D architectures with (66)2(64 ·82) and (52 ·8)(54 ·6∙8)(4·53 ·62 ·7·82 ·10) Schläfli symbols, respectively. Their thermal and photoluminescent properties were also investigated. [ABSTRACT FROM AUTHOR]

Reactions of PbI2 with KI, I2 and 1,2-bis(diphenylphosphino)ethane (dppe) (molar ratio=1:5:3:4) in MeCN/EtOH under solvothermal conditions afforded a one-dimensional (1D) coordination polymer [(EP)(Pb2I6)]n (EP2+ =ethane-1,2-diylbis(ethyldiphenylphosphonium)) (1) and a three-dimensional (3D) coordination polymer [{(Pb3(μ-I)6)(dppeo)3}·EtOH]n (2) (by-product). Treatment of the same components with H2O2 under similar conditions produced another 3D coordination polymer [{Pb2(μ-I)2(μ3-I)2}(dppeo)]n (dppeo=ethane-1,2-diylbis(diphenylphosphine oxide)) (3). Compound 2 could also be prepared in a medium yield from solvothermal reactions of PbI2 with KI, I2 and dppeo (molar ratio=1:5:3:4). Compounds 1–3 were characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 contains one 1D anionic [PbI3]n n− chain with EP2+ dications being embedded between chains. The EP2+ dication was in situ generated via the cleavage of C O bond of EtOH followed by alkylation of dppe. Compound 2 consists of trinuclear [Pb3(μ-I)6] fragments that are interlinked via dppeo bridges to form a 3D 6-connected net (a 41263 Schläfli symbol). Compound 3 has a 3D net (with a 66 Schläfli symbol) constructed from 1D [Pb2(μ-I)2(μ3-I)2]n chains linked by dppeo ligands. The dppeo ligand in 3 was formed in situ from the oxidation of dppe by H2O2. The optoelectronic properties of 1–3 were also investigated. [ABSTRACT FROM AUTHOR]

Reactions of N,N-bis(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) with [Ag(MeCN)4]ClO4 or AgX (X = Cl, Br, I, SCN, CN) afforded a family of oligomeric and polymeric complexes: [Ag2(MeOH)(bdppmapy)2](ClO4)2 (1), [AgCl(bdppmapy)] (2), [AgBr(bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN(bdppmapy)] (5), [{(η2-bdppmapy)Ag(μ-CN)AgCN}2(μ-bdppmapy)] (6), [Ag4(μ-CN)4(μ-bdppmapy)] (7), and [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-CN)6] (8). Compounds 1–8 were characterized by elemental analyses, IR spectra, 1H and 31P{1H} NMR, electrospray ionization (ESI) mass spectra, powder X-ray diffraction (XRD), and single-crystal X-ray diffraction. Compounds 1–3 and 5 hold a one-dimensional (1D) chain in which [Ag(MeOH)]+ or [AgX] motifs are linked by bdppmapy bridges. Compound 6 has a tetrameric framework in which two linear [(η2-bdppmapy)Ag(μ-CN)AgCN] fragments are connected by a μ-bdppmapy ligand. Compound 7 contains a 1D staircase chain in which two zigzag [Ag(μ-CN)]n chains are linked by pairs of μ-bdppmapy bridges. Compound 8 possesses an unprecedented three-dimensional (3D) structure in which the channels of one 3D anionic [Ag10(μ-CN)12]n2n– net are plugged with 1D cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chains. The degradation versus expansion of the bulk AgX frameworks do affect the formation of [AgaXb]-based oligomers and polymers when AgX is treated with bdppmapy. The photoluminescent properties of 1–8 in the solid state were also investigated. Treatment of [Ag(MeCN)4]ClO4 or AgX (X = Cl, Br, I, SCN, CN) with N,N-bis(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) gave rise to a set of oligomeric and polymeric complexes: [Ag2(MeOH)(bdppmapy)2](ClO4)2 (1), [AgCl(bdppmapy)] (2), [AgBr (bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN(bdppmapy)] (5), [{(η2-bdppmapy)Ag(μ-CN)AgCN}2(μ-bdppmapy)] (6), [Ag4(μ-CN)4(μ-bdppmapy)] (7), and [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-CN)6] (8). Compounds 1−8 were characterized by elemental analyses, IR spectra, 1H and 31P{1H} NMR, electrospray ionization (ESI) mass spectra, powder X-ray diffraction (XRD), and single-crystal X-ray diffraction. The photoluminescent properties of 1−8 in the solid state were also investigated. [ABSTRACT FROM AUTHOR]

Abstract: The solvothermal reactions of Zn(NO3)2∙6H2O with 1,4-benzenedicarboxylic acid (1,4-H2bdc) and 1,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)butane (dmpzb) or 1,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)hexane (dmpzh) afforded two three-dimensional coordination polymers [Zn3(1,4-bdc)3(dmpzb)] n (1) and [Zn2(1,4-bdc)2(dmpzh)] n (2), respectively. Compounds 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single crystal X-ray diffraction. Compound 1 has an 8-connected 3D net (a 364185262 Schläfli symbol) assembled from trinuclear [Zn3(1,4-bdc)3] units and 1,4-bdc and dmpzb bridges. Compound 2 has a 6-connected 3D net (with a 485463 Schläfli symbol) constructed from binuclear [Zn2(1,4-bdc)2] units and 1,4-bdc and dmpzh linkers. The solid state luminescent and thermal stability properties of 1 and 2 at ambient temperature were also investigated. The results showed that the spacer lengths of bipyrazol-based ligands did affect the topological structures of zinc(II) coordination polymers. [Copyright &y& Elsevier]

Abstract: The cyclotrimerization of aryl isocyanates and the cyclodimerization of alkyl isocyanates initiated by one praseodymium benzenethiolate complex [Pr(SPh)3(THF)3] were investigated. Comparative runs with [Pr(SPh)3(THF)3] and its precursor Pr[(Me3Si)2N]3 showed that the former has the advantages of a higher selectivity toward isocyanates, easy preparation, low catalyst loading, high conversion as well as mild reaction conditions. [Copyright &y& Elsevier]

Abstract: The chemistry of metal complexes of the zwitterionic ammonium thiolates has expanded dramatically in the recent years. This review is intended to summarize the synthesis and crystal structures of groups 11 and 12 metal zwitterionic ammonium thiolate complexes. Seven methods for the synthesis of these metal complexes of the zwitterionic ammonium thiolates are outlined: proton transfer reaction, precursor reaction, ligand exchange reaction, oxidation–reduction reaction, solid-state reaction, electrochemical reaction and hydro(solvo)thermal reaction. These metal complexes of the zwitterionic ammonium thiolates are classified according to the number of metal atoms; their specific structures are briefly discussed. [Copyright &y& Elsevier]

Abstract: Reactions of [PPh4][(η5-C5Me5)WS3] with equimolar M′Cl2 (M′=Zn, Cd) in MeCN or 0.5equiv. of HgCl2 in DMF afforded two binuclear clusters [PPh4][(η5-C5Me5)WS3(M′Cl2)] (1: M′=Zn; 2: M′=Cd) and one trinuclear cluster [{(η5-C5Me5)WS3}2Hg] (3). Compounds 1–3 were characterized by elemental analysis, IR, UV–Vis, 1H NMR and X-ray crystallography. Compound 1 may be viewed as a 1:1 composite of [PPh4][(η5-C5Me5)WS3] and ZnCl2, in which one [(η5-C5Me5)WS3]− anion binds a ZnCl2 moiety via two μ-S atoms. In the structure of 3, two [(η5-C5Me5)WS3]− anions coordinate the central Hg atom via two μ-S atoms, forming an unique bent linear structure. In addition, internal redox reactions of [PPh4][(η5-C5Me5)WS3] under the presence of M′Cl2 (M′=Zn, Cd, Hg) in high concentrations were discussed. [Copyright &y& Elsevier]