Synthesis of Cyclopropanes via Organoiron Methodology: Preparation of \u3cem\u3erac\u3c/em\u3e-Dysibetaine Cpa

The cyclopropane containing betaine, rac-dysibetaine CPa, was prepared from (1-methoxycarbonylpentadienyl)-Fe(CO)2PPh3+ by nucleophilic addition of nitromethane anion followed by oxidatively induced reductive elimination

The Crystal and Molecular Structure of a Trifluoroacetylacetonate Complex of Scandium, Sc(CH\u3csub\u3e3\u3c/sub\u3eCOCHCOCF\u3csub\u3e3\u3c/sub\u3e)\u3csub\u3e3\u3c/sub\u3e

The crystal and molecular structure of Sc(CH3COCHCOCF3)3 has been determined by X-ray diffraction. The compound crystallizes as pure mer-isomer in the orthorhombic space group Pbca with lattice parameters a=15.166(8) Å, b=13.560(7) Å, c=19.327(10) Å, α=β=γ=90°, V=3974(4) Å3, Z=8. The complex at 100 K is partially disordered in the crystal structure in an approximate 5:1 ratio with 83% fluorine population at C-11 and 17% at C-15. NMR data is compared to that previously reported

Crystal and molecular structure of bis(8-phenylmenthyl) 2-(2-methyl-5-oxo-3-cyclohexen-1-yl)propandioate, C\u3csub\u3e42\u3c/sub\u3eH\u3csub\u3e54\u3c/sub\u3eO\u3csub\u3e5\u3c/sub\u3e• CH\u3csub\u3e3\u3c/sub\u3eCN

The X-ray crystal structure of the title compound, as crystallized from acetonitrile-water was determined. The relative stereochemistry of the cyclohexenone ring with respect to the 8-phenylmenthyl esters was determined. The title compound crystallizes in the noncentrosymmetric space group P21, with a=8.9850(10) Å, b=15.575(3) Å, c=14.478(2) Å, β=94.61(2)°, and D calc=1.118 g cm−3 for Z=2

5,7-Dibromo-3-trifluoro­methyl-3,4-dihydro­acridin-1(2H)-one

In the title compound, C14H8Br2F3NO, the mol­ecule is disordered across an approximate non-crystallographic mirror plane, which is in the plane of the fused ring system [The tetrahedral C atom bearing the trifluormethyl substituent is disordered with site occupancy factors of 0.80 (2) and 0.20 (2)]. In the crystal, a one-dimensional stacking of mol­ecules involves inter­actions between the pyridine ring and symmetry-related Br and O atoms of adjacent mol­ecules. The stacking distance between the mean planes of adjacent mol­ecules is 3.395 (4) Å

Synthesis of Some New Fluorinated Hexahydroquinoline and Acridinedione Derivatives in Trifluoroethanol

This article describes one-pot synthesis of new fluorinated hexahydroquinoline derivatives via unsymmetric Hantzsch reaction involving 5-trifluoromethyl-1,3-cyclohexanedione, aldehydes, acetoacetate ester, and ammonium acetate in trifluoroethanol (TFE). The reaction is simple and rapid with high yield

Preparation, Characterization and Reactivity of (3-Methylpentadienyl)iron(1+) Cations

The title cations (9 and 12) were prepared by dehydration of (3-methyl-2,4-pentadien-1-ol)Fe(CO)2L+ complexes. The structure of the (CO)2PPh3-ligated 12 was determined by single-crystal X-ray analysis. Reaction of carbon and heteroatom nucleophiles to (3-methylpentadienyl)Fe(CO)3+ cations 9 and 12 proceeds either via attack at the dienyl terminus to give (3-methyl-1,3Z-diene)iron complexes or via attack at the internal carbon, followed by carbon monoxide insertion and reductive elimination to afford 3-methyl-4-substituted cyclohexenones. Cyclohexenone formation was found to be prevalent for addition of stabilized nucleophiles with strongly dissociated counterions to cation 9 (L = CO). Reaction of cation 9 with sodium bis[(−)-8-phenylmenthyl] malonate gave a single diastereomeric cyclohexenone

Host–Guest Complex of β-Cyclodextrin and Disulfide Form of 4-Aminothiophenol

An inclusion complex of β-cyclodextrin and 4-aminothiophenol was assembled by hydrophobic interaction of the host (β-cyclodextrin) and guest (4-aminothiophenol). The complex was isolated as crystalline solid and studied by single crystal X-ray diffraction method along with NMR and IR spectroscopy. Two cyclodextrin rings each containing one disulfide form of 4-aminothiophenol were found to pair up by hydrogen bonding of the outer rim -OH groups. The phenyl disulfide moiety of 4-aminophenyl disulfide molecule was found in the core of β-cyclodextrin, while the amino functional groups were positioned to the exterior of the cyclodextrin ring. Phenyl rings of the guest molecule from each partner of the paired cyclodextrin complex were found parallel to each other, indicating possible π-π stacking interaction between them

Synthesis and reactivity of tricarbonyl(1-methoxycarbonyl-5-phenylpentadienyl)iron(1+) cation

Tricarbonyl(1-methoxycarbonyl-5-phenylpentadienyl)iron(1+) hexafluorophosphate (7) was prepared in two steps from tricarbonyl(methyl 6-oxo-2,4-hexadienoate)iron. While addition of carbon and heteroatom nucleophiles to 7 generally occurs at the phenyl-substituted dienyl carbon to afford (2,4-dienoate)iron products, the addition of phthalimide proceeded at C2 to afford a (pentenediyl)iron product (18). Complex 18 was structurally characterized by X-ray diffraction analysis. The reaction of the title cation with carbon and heteroatom nucleophiles was examined. In general, the products arise from nucleophilic attack at C5 to give E,E- or E,Z-dienoate iron complexes. Addition of phthalimide anion proceeds at C2 of the cation to afford a (pentenediyl)iron complex, whose structure was confirmed by X-ray diffraction analysis

P–C and C–H Bond Cleavages of dppm in the Thermal Reaction of [Ru\u3csub\u3e3\u3c/sub\u3e(CO)\u3csub\u3e10\u3c/sub\u3e(μ-dppm)] with Benzothiophene: X-ray structures of [Ru\u3csub\u3e6\u3c/sub\u3e(μ-CO)(CO)\u3csub\u3e13\u3c/sub\u3e{μ\u3csub\u3e4\u3c/sub\u3e-PhP(C\u3csub\u3e6\u3c/sub\u3eH\u3csub\u3e4\u3c/sub\u3e)PPh}(μ\u3csub\u3e6\u3c/sub\u3e-C)] and [Ru\u3csub\u3e4\u3c/sub\u3e(CO)\u3csub\u3e9\u3c/sub\u3e(μ\u3csub\u3e3\u3c/sub\u3e-η\u3csup\u3e2\u3c/sup\u3e-PhPCH\u3csub\u3e2\u3c/sub\u3ePPh\u3csub\u3e2\u3c/sub\u3e)(μ\u3csub\u3e4\u3c/sub\u3e-η\u3csup\u3e6\u3c/sup\u3e:η\u3csup\u3e1\u3c/sup\u3e:η\u3csup\u3e1\u3c/sup\u3e-C\u3csub\u3e6\u3c/sub\u3eH\u3csub\u3e4\u3c/sub\u3e)(μ-H)]

The thermal reaction of [Ru3(CO)10(μ-dppm)] (1) with benzothiophene in refluxing toluene gives a complex mixture of products. These include the known compounds [Ru2(CO)6{μ-CH2PPh(C6H4)PPh}] (2), [Ru2(CO)6{μ-C6H4PPh(CH2)PPh}] (3), [Ru3(CO)9{μ3-η3-(Ph)PCH2P(Ph)C6H4}] (4) and [Ru3(CO)10{μ-η2-PPh(CH2)(C6H4)PPh}] (6), as well as the new clusters [Ru6(μ-CO)(CO)13{μ3-η2-PhP(C6H4)PPh}(μ6-C)] (5) and [Ru4(CO)9(μ3-η2-PhPCH2PPh2)(μ4-η6:η1:η1-C6H4)(μ-H)] (7). The solid-state molecular structures of 5 and 7 were confirmed by single crystal X-ray analyses. Compound 5 consists of interesting example of a hexaruthenium interstitial carbido cluster having a tetradentate diphosphine ligand derived from the activation of P–C and C–H bonds of the dppm ligand in 1. The tetranuclear compound 7 consists of a unique example of a non-planar spiked triangular metal fragment of ruthenium [Ru(1), Ru(2) and Ru(3)] unit with Ru(4) being bonded to Ru(1). The μ4-η1:η6:η1-benzyne ligand in this compound represents a previously uncharacterized bonding mode for benzyne. Compounds 5 and 7 do not contain any benzothiophene-derived ligand. The reaction of 4 with benzothiophene gives 2, 3, 5 and 6. Thermolysis of 1 in refluxing toluene gives 2, 3 and 4; none of 5 and 7 is detected in reaction mixture

Decarbonylation Reaction of [Os\u3csub\u3e3\u3c/sub\u3e(CO)\u3csub\u3e10\u3c/sub\u3e(\u3cem\u3eμ\u3c/em\u3e-H)(\u3cem\u3eμ\u3c/em\u3e-SN\u3csub\u3e2\u3c/sub\u3eC\u3csub\u3e4\u3c/sub\u3eH\u3csub\u3e5\u3c/sub\u3e)]: X-ray Structures of the Two Isomers of [Os\u3csub\u3e3\u3c/sub\u3e(CO)\u3csub\u3e9\u3c/sub\u3e(\u3cem\u3eμ\u3c/em\u3e-H)(\u3cem\u3eμ\u3c/em\u3e\u3csub\u3e3\u3c/sub\u3e-\u3cem\u3eη\u3c/em\u3e\u3csup\u3e2\u3c/sup\u3e-SN\u3csub\u3e2\u3c/sub\u3eC\u3csub\u3e4\u3c/sub\u3eH\u3csub\u3e5\u3c/sub\u3e)]

The thermal reaction of [Os3(CO)10(μ-H)(μ-SN2C4H5)] (1) at 110 °C afforded the new compound [Os3(CO)9(μ-H)(μ 3-η 2-SN2C4H5)] (2) in 84% yield. Compound 2 exists as two isomers, which differ in the disposition of the bridging hydride ligand. Both of the isomers of 2 have been characterized by a combination of elemental analysis, infrared and 1H NMR spectroscopic data together with single crystal X-ray crystallography. The isomers crystallize together in the triclinic space group P-1 with a = 10.4775(2), b = 13.3056(3), c = 15.0325(3) Å, α = 110.8890(10), β = 99.3880(10), γ = 96.1620(10)°, Z = 2 and V = 1900.31(7) Å3