2‐Trichloromethylthio‐1H‐iso­indole‐1,3(2H)‐dione (Folpet)

The title compound (C₉H₄Cl₃NO₂S), commonly known as Folpet, belongs to a group of phthalimides which function as fungicides or can be used in the laboratory as sulfurizing agents. The phthalimide moiety is slightly folded with a dihedral angle of 3.5 (4)°. The molecule participates in C—H?O and Cl?Cl intermolecular interactions.     

Hexakis(prop‐2‐enamide)copper(II) bis(perchlorate) and hexakis(prop‐2‐enamide)manganese(II) bis(perchlorate)

The structures of [Cu(AA)₆](ClO₄)₂, (I), and [Mn(AA)₆](ClO₄)₂, (II) (AA is acrylamide, also known as prop‐2‐enamide; C₃H₅NO), display both intra‐ and intermolecular N—H...O hydrogen bonding. A three‐dimensional network is propagated via the perchlorate counter‐ions. There are two crystallographically independent molecules in the copper complex, with the most significant difference between them being the conformation of one symmetry‐related pair of AA ligands which are in the unusual syn conformation. The copper complex exhibits syn/anti disorder of the =CH₂ group in one pair of symmetry‐related AA ligands. The Cu^II and Mn^II centres are both situated on centres of inversion. The copper complex cation has octahedral coordination geometry with typical Jahn–Teller distortions.     

(2E)‐N‐(2‐Iodo‐4,6‐dimethylphenyl)‐2‐methylbut‐2‐enamide

The title compound, C₁₄H₁₈INO, crystallizes as +sc/+sp/+sc 2‐iodoanilide molecules (and racemic opposites) and shows significant intermolecular I...O interactions in the solid state, forming dimeric pairs about centres of symmetry. Under asymmetric Heck conditions, the S enantiomer of the dihydroindol‐2‐one was obtained using (R)‐(+)‐2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl [(R)‐BINAP], suggesting a mechanism that proceeds by oxidative addition to give the title (P) enantiomer of the compound and pro‐S coordination of the Re face of the alkene in a conformation similar to that defined crystallographically, except that rotation about the C—C bond of the butenyl group is required.     

Tetrabromo(2‐methylpyridine‐N)titanate(IV)

The reaction of 2‐methyl­pyridine with TiBr₄ affords tetra­bromo(2‐methyl­pyridine‐N)­titanate(IV), C₆H₇Br₄NTi. The environment around the Ti atom can be described as a slightly distorted trigonal bipyramid, with the nitro­gen base occupying an equatorial position. The crystal structure of the title compound is isomorphous with tetra­chloro(2‐methyl­pyridine‐N)­titanate(IV).     

Polymeric (3‐amino‐2‐chloropyridine)nitratosilver(I)

In the title compound {alternative name: poly­[silver(I)‐μ‐(3‐­amino‐2‐chloro­pyridine)‐μ‐nitr­ato]}, [Ag(NO₃)(C₅H₅ClN₂)]_n the Ag^I atom is in an irregular AgN₂O₃ geometry, surrounded by one pyridyl N atom [Ag—N 2.283 (5) Å], one amine N atom [Ag—N 2.364 (6) Å] and three O atoms from different nitrate ions [Ag—O 2.510 (6)–2.707 (6) Å]. The Ag ions are bridged by the 3‐amino‐2‐chloro­pyridine ligands into helical chains. Adjacent uniform chiral chains are further interlinked through the NO₃ bridges into an interesting two‐dimensional coordination network in the solid.     

Regioselective ortho‐Metallation of 2‐Diphenylphosphanylpyridine and (2‐(2‐Diphenylphosphanyl)phenyl)‐1‐3‐dioxalane with Methyltetrakis(trimethylphosphane)cobalt(I)

Co(CH₃)(PMe₃)₄ forms 100 % regioselectively with (2‐(2‐diphenylphosphanyl)phenyl)‐1,3‐dioxalane and 2‐diphenylphosphanyl‐pyridine, by elimination of methane, the four‐membered metallacycles Co{(C₃O₂HC₆H₃)P(C₆H₅)₂}(PMe₃)₃ ( 1 ) and Co{(CNC₄H₃)P(C₆H₅)₂}(PMe₃)₃ ( 4 ). The regioselectivity is independent of the steric requirement of the ortho substituent in the 2‐diphenylphosphanylaryl‐ligands. Oxidative addition with iodomethane transforms 1 and 4 into octahedral, diamagnetic low‐spin d⁶ complexes Co(CH₃)I‐{(C₃O₂HC₆H₃)P(C₆H₅)₂}(PMe₃)₂ ( 2 ) and Co(CH₃)I‐{(CNC₄H₃)P(C₆H₅)₂}(PMe₃)₂ ( 5 ). Under an atmosphere of carbon monoxide, insertion into the Co‐C bond results in ring expansion by forming the new assembled phosphanylbenzoyl complexes Co{(C₄O₃HC₆H₃)‐P(C₆H₅)₂}CO(PMe₃)₂ ( 3 ) and Co{(OCNC₄H₃)P(C₆H₅)₂}CO(PMe₃)₂ ( 6 ). The three different types of cobaltacycles are supported by X‐ray diffraction of 1 , 3 , 5 and 6 .     

(2‐Amino­ethoxy)­bis(2‐thienyl)­boron

In the five‐membered ring in the title compound, (2‐amino­ethoxy)­bis(2‐thienyl)­boron, C₁₀H₁₂BNOS_2, the B atom is four‐coordinate with dimensions N—B 1.654 (3), O—B 1.479 (3), and C—B 1.606 (3) and 1.609 (3) Å. An intermolecular hydrogen bond between an amino H atom and the ethoxy O atom links the mol­ecules into infinite chains along the a axis. Only one of the two amino H atoms is involved in hydrogen bonding because there is only the one acceptor atom, the ethoxy O atom, and the molecular geometry precludes formation of a second hydrogen bond by the second amino H atom.     

Pentacarbonyl(di‐2‐pyridyl­amine)tungsten(0)

In the title molecular complex, (I), the W atom is in an octahedral environment with four equatorial carbonyl ligands and a fifth in an axial position trans to the monodentate dipyridyl­amine ligand. The long dimension of this last bisects the angle between two of the equatorial carbonyl groups and while the non‐bonded pyridyl N atom is directed away from the W atom, the bridging amine group is directed towards it. Thus, in addition to the N atom to which it is attached, the amino H has two nearest neighbour C atoms of equatorial carbonyl groups but does not participate in hydrogen bonding in any real or usual sense. The W—C bond distance for the axial carbonyl group is notably less than those of the equatorial groups.     

Hierarchical Self‐Assembly of Double‐Crystalline Poly(ferrocenyldimethylsilane)‐block‐poly(2‐iso‐propyl‐2‐oxazoline) (PFDMS‐b‐PiPrOx) Block Copolymers

The step‐wise solution self‐assembly of double crystalline organometallic poly(ferrocenyldimethylsilane)‐block‐poly(2‐iso‐propyl‐2‐oxazoline) (PFDMS‐b‐PiPrOx) diblock copolymers is demonstrated. Two block copolymers are obtained by copper‐catalyzed azide‐alkyne cycloaddition (CuAAC), featuring PFDMS/PiPrOx weight fractions of 46/54 (PFDMS₃₀‐b‐PiPrOx₇₅) and 30/70 (PFDMS₃₀‐b‐PiPrOx₁₅₅). Nonsolvent induced crystallization of PFDMS in acetone leads in both cases to cylindrical micelles with a PFDMS core. Afterward, the structures are transferred into water for sequential temperature‐induced crystallization of the PiPrOx corona, leading to hierarchical double crystalline superstructures, which are investigated using scanning electron microscopy, wide angle X‐ray scattering, and differential scanning calorimetry.

     

Mononuclear nickel(II) and zinc(II) complexes with deprotonated forms of the tripodal hexadentate ligand 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine

In the crystal structures of both title compounds, [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]nickel(II) [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]nickel(II) chloride methanol disolvate, [Ni(C₂₆H_25.5N₃O₃)]₂Cl·2CH₄O, and [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]zinc(II) perchlorate [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]zinc(II) methanol trisolvate, [Zn(C₂₆H₂₅N₃O₃)]ClO₄·[Zn(C₂₆H₂₆N₃O₃)]·3CH₄O, the 3d metal ion is in an approximately octahedral environment composed of three facially coordinated imine N atoms and three phenol O atoms. The two mononuclear units are linked by three phenol–phenolate O—H...O hydrogen bonds to form a dimeric structure. In the Ni compound, the asymmetric unit consists of one mononuclear unit, one‐half of a chloride anion and a methanol solvent molecule. In the O—H...O hydrogen bonds, two H atoms are located near the centre of O...O and one H atom is disordered over two positions. The Ni^II compound is thus formulated as [Ni(H_1.5L)]₂Cl·2CH₃OH [H₃L is 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine]. In the analogous Zn^II compound, the asymmetric unit consists of two crystallographically independent mononuclear units, one perchlorate anion and three methanol solvent molecules. The mode of hydrogen bonding connecting the two mononuclear units is slightly different, and the formula can be written as [Zn(H₂L)]ClO₄·[Zn(HL)]·3CH₃OH. In both compounds, each mononuclear unit is chiral with either a Δ or a Λ configuration because of the screw coordination arrangement of the achiral tripodal ligand around the 3d metal ion. In the dimeric structure, molecules with Δ–Δ and Λ–Λ pairs co‐exist in the crystal structure to form a racemic crystal. A notable difference is observed between the M—O(phenol) and M—O(phenolate) bond lengths, the former being longer than the latter. In addition, as the ionic radius of the metal ion decreases, the M—O and M—N bond distances decrease.     

Synthesis of (2S)‐2‐(Benzoylamino)‐3‐(heteroaryl)propyl Benzoates

(3E,5S)‐1‐Benzoyl‐5‐[(benzoyloxy)methyl]‐3‐[(dimethylamino)methylidene]pyrrolidin‐2‐one ( 9 ) was prepared in two steps from commercially available (S)‐5‐(hydroxymethyl)pyrrolidin‐2‐one ( 7 ) (Scheme 1). Compound 9 gave, in one step, upon treatment with various C,N‐ and C,O‐1,3‐dinucleophiles 10 – 18 , the corresponding 3‐(quinolizin‐3‐yl)‐ and 3‐(2‐oxo‐2H‐pyran‐3‐yl)‐substituted (2S)‐2‐(benzoylamino)propyl benzoates 19 – 27 (Schemes 1 and 2).     

A highly efficient synthesis of (Z)‐1‐aryl‐2‐silyl‐1‐ stannylethenes and their conversion to (E)‐2‐ arylethenyl‐, (Z)‐2‐(2‐pyridyl)ethenyl‐ and allenyl‐silanes

A Pd(dba)₂–P(OEt)₃ combination allowed the silastannation of arylacetylenes, 1‐hexyne or propargyl alcohols with tributyl(trimethylsilyl)stannane to take place at room temperature, producing (Z)‐2‐silyl‐1‐stannyl‐1‐substituted ethenes in high yields. Novel silyl(stannyl)ethenes were fully characterized by ¹H‐, ¹³C‐, ²⁹Si‐ and ¹¹⁹Sn‐NMR as well as infrared and mass analyses. Treatment of a series of (Z)‐1‐aryl‐2‐silyl‐1‐stannylethenes and (Z)‐1‐(3‐pyridyl)‐2‐silyl‐1‐stannylethene with hydrochloric acid or hydroiodic acid in the presence of tetraethylammonium chloride (TEACl) or tetrabutylammonium iodide (TBAI) led to the exclusive formation of (E)‐trimethyl(2‐arylethenyl)silanes with high stereoselectivity. A similar reaction of (Z)‐1‐(2‐anisyl)‐2‐silyl‐1‐stannylethene also produced E‐type trimethyl[2‐(2‐anisyl)ethenyl]silane, while (Z)‐trimethyl [2‐(2‐pyridyl)ethenyl]silane was produced exclusively from (Z)‐1‐(2‐pyridyl)‐2‐silyl‐1‐stannylethene. Protodestannylation of (Z)‐1‐[hydroxy(phenyl)methyl]‐2‐silyl‐1‐stannylethene with trifluoroacetic acid took place via the β‐elimination of hydroxystannane, providing trimethyl(3‐phenylpropa‐1,2‐dienyl)silane quite easily. The destannylation products were also fully characterized. Copyright © 2007 John Wiley & Sons, Ltd.     

Molecular Structures of Dibromo[(E)2‐bromo‐2‐phenylvinyl]‐(phenyl) tellurium (IV) and Dibromo [(Z)‐2‐bromo‐2‐phenyl‐vinyl] (p‐tulyl) tellurium (IV) hydrate methanolate

The structures of title compounds, [TeBr₂(C₈H₆Br)(C₆H₅)] (I) and [TeBr₂(C₈H₆Br)(C₇H₉)](H₂O)(CT₃OH) (II), have been determined by X‐ray diffraction. The structures confirm that E‐ or Z‐type configuration of vinylic telluride depends on the polarity of solvent employed. In either structure, Te atom is in a trigonal dipyramide configuration with the lone pair of electrons in the equatorial position.     

Two Novel Three‐Dimensional Lead(II) Coordination Polymers Involving 16‐Membered Rings: [Pb2(Bs‐glu)2(bipy)2] and [Pb2(Bs‐glu)2(phen)2]

The reaction of Pb(CH₃COO)₂·3H₂O with N‐benzesulfonyl‐L‐glutamic acid in the presence of 2, 2′‐bipyridine (bipy) or 1,10‐phenanthroline (phen) produced two novel complexes [Pb₂(Bs‐glu)₂(bipy)₂] ( 1 ) and [Pb₂(Bs‐glu)₂(phen)₂] ( 2 ) (Bs‐glu = N‐benzesulfonyl‐L‐glutamic acid dianion). In 1 chains bearing alternative 16‐membered rings and Pb₂O₃ nodes are constructed from the interactions of Pb^II ions with the carboxylates of Bs‐glu ligands. To the best of our knowledge, this is the first lead(II) complex of carboxylates with the formation of chains of Pb₂O₃. In 2 the 16‐membered ring units are connected by centrosymmetric Pb₂O₂ nodes to form chains. Complexes 1 and 2 construct the 3‐D supramolecular architectures through versatile hydrogen bonds and π‐π stacking interactions.     

(2S)‐1‐Carbamoylpyrrolidine‐2‐carboxylic acid

In the title compound, also known as N‐carbamoyl‐l ‐proline, C₆H₁₀N₂O₃, the pyrrolidine ring adopts a half‐chair conformation, whereas the carboxyl group and the mean plane of the ureide group form an angle of 80.1 (2)°. Molecules are joined by N—H...O and O—H...O hydrogen bonds into cyclic structures with graph‐set R²₂(8), forming chains in the b‐axis direction that are further connected via N—H...O hydrogen bonds into a three‐dimensional network.     

2‐(Diphenylphosphinoylmethyl)pyrrole–2‐(diphenylphosphinomethyl)pyrrole (0.43/0.57) and tetrachlorido(5‐diphenylphosphinomethyl‐2H‐pyrrole‐κ2N,P)titanium(IV)

The title phosphine oxide–phosphine, 0.43C₁₇H₁₆NOP·0.57C₁₇H₁₆NP, (I)/(II), was obtained as a 0.861 (6):1.139 (6) cocrystallized mixture. Hydrogen bonding between the two constituents leads to the formation of 2:2 solid‐state assemblies. Instead of forming the expected simple N,P‐chelated system via loss of the N‐bound H atom, reaction of 2‐(diphenylphosphinomethyl)pyrrole, (II), with TiCl₄ leads to the formation of the title titanium(IV) complex, [TiCl₄(C₁₇H₁₆NP)], (IV), containing a rearranged neutral ligand in which the N‐bound H atom moves to one of the pyrrole C atoms, giving a partially unsaturated ring.     

(E)‐2‐Methyl‐3‐(2‐methyl‐2‐nitro­vinyl)‐1H‐indole and (E)‐3‐(2‐methyl‐2‐nitro­vinyl)‐2‐phenyl‐1H‐indole

In the title compounds, C₁₂H₁₂N₂O₂, (I), and C₁₇H₁₄N₂O₂, (II), respectively, the indole rings are planar and the vinyl groups lie out of the indole planes, making dihedral angles of 33.48 (5) and 41.31 (8)°, respectively. In (II), the dihedral angle between the phenyl and indole ring planes is 32.06 (6)°. In both mol­ecules, the double bond connecting the methyl­nitro­vinyl group and the indole nucleus adopts an E configuration. Notwithstanding the differences in space group [C2/c for (I) and P2₁2₁2₁ for (II)], the mode of packing of compounds (I) and (II) is determined by similar inter­molecular N—H⋯O hydrogen‐bonding inter­actions, forming chains that run parallel to [101] in (I) and [001] in (II).     

(Benzoxazole‐2‐thiol­ato‐S)(benzoxazole‐2‐thione‐S)­bis­(tri­phenylphosphine)copper(I)

The Cu atom in [Cu(C₇H₄NOS)(C₇H₅NOS)(C₁₈H₁₅P)₂] is tetrahedrally coordinated by a P₂S₂ donor set. One S atom is derived from neutral benzoxazole‐2‐thione and the other from the deprotonated form of the ligand. The two sulfur ligands are connected via an N—H?N interaction, leading to the formation of an eight‐membered ring.     

(1,3‐Dimethylimidazolidine‐2‐selone‐κSe)bis(1,10‐phenanthroline‐κ2N,N′)copper(II) bis(perchlorate) and bis(2,2′‐bipyridyl‐κ2N,N′)(imidazolidine‐2‐thione‐κS)copper(II) bis(perchlorate)

In the first title salt, [Cu(C₁₂H₈N₂)₂(C₅H₁₀N₂Se)](ClO₄)₂, the Cu^II centre occupies a distorted trigonal–bipyramidal environment defined by four N donors from two 1,10‐phenanthroline (phen) ligands and by the Se donor of a 1,3‐dimethylimidazolidine‐2‐selone ligand, with the equatorial plane defined by the Se and by two N donors from different phen ligands and the axial sites occupied by the two remaining N donors, one from each phen ligand. The Cu—N distances span the range 1.980 (10)–2.114 (11) Å and the Cu—Se distance is 2.491 (3) Å. Intermolecular π–π contacts between imidazolidine rings and the central rings of phen ligands generate chains of cations. In the second salt, [Cu(C₁₀H₈N₂)₂(C₃H₆N₂S)](ClO₄)₂, the Cu^II centre occupies a similar distorted trigonal–bipyramidal environment comprising four N donors from two 2,2′‐bipyridyl (bipy) ligands and an S donor from an imidazolidine‐2‐thione ligand. The equatorial plane is defined by the S donor and two N donors from different bipy ligands. The Cu—N distances span the range 1.984 (6)–2.069 (7) Å and the Cu—S distance is 2.366 (3) Å. Intermolecular π–π contacts between imidazolidine and pyridyl rings form chains of cations. A major difference between the two structures is due to the presence in the second complex of two N—H...O hydrogen bonds linking the imidazolidine N—H hydrogen‐bond donors to perchlorate O‐atom acceptors.     

MAO‐free polymerization of propylene by rac‐ Me2Si(1‐C5H2‐2‐Me‐4‐tBu)2Zr(NMe2)2 compound

Ansa‐zirconocene diamide complex rac‐Me₂Si(CMB)₂Zr(NMe₂)₂ (rac‐1, CMB = 1‐C₅H₂‐2‐Me‐4‐^tBu) reacts with AlR₃ (R = Me, Et, i‐Bu) and then with [CPh₃]⁺[B(C₆F₅)₄]⁻ (2) in toluene in order to in situ generate cationic alkylzirconium species. In the sequential NMR‐scale reactions of rac‐1 with various amount of AlMe₃ and 2, rac‐1 transforms first to rac‐Me₂Si(CMB)₂Zr(Me)(NMe₂) (rac‐3) and rac‐Me₂Si(CMB)₂ZrMe₂ (rac‐4) by the reaction with AlMe₃, and then to [rac‐Me₂Si(CMB)₂ZrMe]⁺ (5⁺) cation by the reaction of the resulting mixtures with 2. The activities of propylene polymerizations by rac‐1/Al(i‐Bu)₃/2 system are dependent on the type and concentration of AlR₃, resulting in the order of activity: rac‐1/Al(i‐Bu)₃/2 > rac‐1/AlEt₃/2 > rac‐1/MAO ≫ rac‐1/AlMe₃/2 system. The bulkier isobutyl substituents make inactive catalytic species sterically unfavorable and give rise to more separated ion pairs so that the monomers can easily access to the active sites. The dependence of the maximum rate (R_{p, max}) on polymerization temperature (T_p) obtained by rac‐1/Al(i‐Bu)₃/2 system follows Arrhenius relation, and the overall activation energy corresponds to 0.34 kcal/mol. The molecular weight (MW) of the resulting isotactic polypropylene (iPP) is not sensitive to Al(i‐Bu)₃ concentration. The analysis of regiochemical errors of iPP shows that the chain transfer to Al(i‐Bu)₃ is a minor chain termination. The 1,3‐addition of propylene monomer is the main source of regiochemical sequence and the [mr] sequence is negligible, as a result the meso pentad ([mmmm]) values of iPPs are very high ([mmmm] > 94%). These results can explain the fact that rac‐1/Al(i‐Bu)₃/2 system keeps high activity over a wide range of [Al(i‐Bu)₃]/[Zr] ratio between 32 and 3,260. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1071–1082, 1999