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.     

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Crystal and molecular structure of a steroidal spirocyclic lactone, C29H34O4

The X-ray crystal structure of the title compound, as crystallized from methanol–methylene chloride was determined. The asymmetric unit contains two steroid molecules, which differ primarily in the orientation of the aromatic rings of the benzyl ethers. The title compound crystallizes in the noncentrosymmetric space group P2(1), with a = 7.558(2), b = 16.673(3), c = 18.735(4) Å, = 97.610(10)°, and D _calc = 1.268 g cm^–1 for Z = 4.     

The crystal and molecular structure of a trifluoroacetylacetonate complex of scandium,Sc(CH<Subscript>3</Subscript>COCHCOCF<Subscript>3</Subscript>)<Subscript>3</Subscript>

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) ?, b=13.560(7) ?, c=19.327(10) ?, α=β=γ=90°, V=3974(4) ?³, 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.     

Separation and identification of volatile compounds from liquid cultures of Trichoderma harzianum by GC-MS using three different capillary columns

A simple, fast, repeatable and less laborious sample preparation protocol was developed and applied for the analysis of biocontrol fungus Trichoderma harzianum strain FA1132 by using gas chromatography-mass spectrometry. The match factors for sample spectra with respect to the mass spectra library of fungal volatile compounds were determined and used to study the complex hydrocarbons and other volatile compounds, which were separated by using different capillary columns with nonpolar, medium polar and high polar stationary phases. To date, more than 278 volatile compounds (with spectral match factor at least 90%) such as normal saturated hydrocarbons (C7-C30), cyclohexane, cyclopentane, fatty acids, alcohols, esters, sulfur-containing compounds, simple pyrane and benzene derivatives have been identified. Most of these compounds have not previously been reported. The method described in this paper is a more convenient research tool for the detection of volatile compounds from the cultures of T. harzianum.     

Reactions of Triruthenium Clusters with Quinolines: X-Ray Structures of [Ru3(μ-CO)(CO)7{μ3-η2-P(C6H5)CH2P(C6H5)2)}{μ-η2-C9H5(CH3)N}] and [Ru3(CO)10(μ-H){μ-η2-C9H6N}]

The reactions of [Ru₃(CO)₁₀(μ-dppm)] 4 with quinolines afforded [Ru₃ (μ-CO)(CO)₇{μ₃-η²-P(C₆H₅)CH₂P(C₆H₅)₂)}{μ-η²-C₉H₅(R)N}] (8, R = 4-Me; 9, R = H) as the major products along with small amounts of known compound [Ru₃(CO)₉{μ₃-η³-P(C₆H₅)CH₂P(C₆H₅)(C₆H₄)}] 5. The molecular structure of 8 has been determined by single crystal X-ray studies. The reaction of 5 with 4-methylquinoline in refluxing cyclohexane afforded 8 and two known dinuclear compounds, [Ru₂(CO)₆{μ-CH₂P(C₆H₅)(C₆H₄)P(C₆H₅}] 10 and [Ru₂(CO)₆ {μ-(C₆H₄)P(C₆H₅)(CH₂)P(C₆H₅}] 11, in 40, 12, and 10% yields, respectively. The compounds 10 and 11 are also formed from the thermolysis of 4 in addition to the major compound 5. The solid state structure of the previously reported [Ru₃(CO)₁₀(η-H){μ-η²-C₉H₆N}] 2a is also reported for comparison.     

Crystal and molecular structure of N-(bicyclo[5.1.0]octa-3,5-dien-2-yl)phthalimide, C16H13NO2

Single crystal X-ray diffraction analysis of the title compound revealed that the phthalimide substituent was endo with respect to the bicyclic ring system.     

Crystal and molecular structure of bis(8-phenylmenthyl) 2-(2-methyl-5-oxo-3-cyclohexen-1-yl)propandioate, C42H54O5· CH3CN

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) ?, b=15.575(3) ?, c=14.478(2) ?, β=94.61(2)°, and D _calc=1.118 g cm⁻³ for Z=2.     

New Mixed‐Metal Carbonyl Complexes Containing Bridging 2‐Mercapto‐1‐methylimidazole Ligand

Reaction of [Mn₂(CO)₁₀] with 2‐mercapto‐1‐methylimidazole in the presence of Me₃NO at 25 °C afforded two new dimanganese complexes [Mn₂(CO)₆(μ‐SN₂C₄H₅)₂] ( 1 ) and [Mn₂(CO)₇(μ‐SN₂C₄H₅)₂] ( 2 ). Compound 1 consists of two μ‐SN₂C₄H₅ ligands, each bound through the sulfur atom to two Mn atoms and through the nitrogen atom to one Mn atom forming a four‐membered chelate ring. Compound 2 was found to consist of one μ‐SN₂C₄H₅ ligand in a similar bonding mode to 1 but another μ‐SN₂C₄H₅ ligand coordinates through the sulfur atom to one Mn atom and through the nitrogen atom to another Mn atom. Compound 1 was also obtained as the only product from the reaction of [Mn₂(CO)₈(NCMe)₂] with 2‐mercapto‐1‐methylimidazole. In contrast, a similar reaction of [Re₂(CO)₈(NCMe)₂] with 2‐mercapto‐1‐methylimidazole led to the formation of the di‐, tri‐, and tetranuclear complexes [Re₃(CO)₈(μ‐CO)(μ₃‐SN₂C₄H₅)₂(μ‐H)] ( 3 ), [Re₄(CO)₁₂(μ‐SN₂C₄H₅)₄] ( 4 ), and [Re₂(CO)₆(μ‐SN₂C₄H₅)₂] ( 5 ). Compound 3 provides a unique example of a hydrido trirhenium compound. The reaction of [Cr(CO)₃(NCMe)₃] and [Mo(CO)₃(NCMe)₃] with 1 in refluxing THF afforded the mixed metal complexes [CrMn₂(CO)₈(μ‐CO)₂(μ₃‐SN₂C₄H₅)₂] ( 6 ) and [MoMn₂(CO)₈(μ‐CO)₂(μ₃‐SN₂C₄H₅)₂] ( 7 ), respectively, in which two Mn–M (M = Mo, Cr) bonds were formed. In contrast, a similar treatment of [W(CO)₃(NCMe)₃] with 1 yielded two W‐Mn complexes [Mn₂W(CO)₈(μ‐CO)₂(μ₃‐SN₂C₄H₅)₂] ( 8 ) and [Mn₂W(CO)₇(μ‐CO)₂(SN₂C₄H₅)(μ₃‐SN₂C₄H₅)₂] ( 9 ). Treatment of 1 with [Fe₃(CO)₁₂] at 70‐75 °C afforded the trinuclear mixed‐metal complex [FeMn₂(CO)₈(μ‐CO)(μ₃‐SN₂C₄H₅)₂] ( 10 ) and the diiron side product [Fe₂(CO)₆(μ‐S₂N₂C₄H₅)₂] ( 11 ). Compounds 6 ‐ 10 have a bent open structure of three metal atoms linked by two metal‐metal bonds and all, except 9 and 10 , contain a noncrystallographic two‐fold axis of symmetry. Compound 9 is structurally similar to 8 , but it contains a SN₂C₄H₆ ligand, mono coordinated through the exocyclic sulfur atom to the W atom and a Mn–Mn bond instead of a Mn–W bond. Compound 11 comprises two bridging S₂N₂C₄H₅ ligands, which arise from the coupling of 2‐mercapto‐1‐methylimidazole with sulfur.     

Dirhenium carbonyl complexes bearing 2-vinylpyridine,morpholine and 1-methylimidazole ligands

Treatment of the labile compound [Re₂(CO)₈(MeCN)₂] with 2-vinylpyridine in refluxing benzene affords exclusively the new compound [Re₂(CO)₈(μ-η¹:η²-NC₅H₄CHCH₂)] (1) in 39% yield in which the μ-η¹:η²-vinylpyridine ligand is coordinated to one Re atom through the nitrogen and to the other Re atom via the olefinic double bond. Reaction of [Re₂(CO)₈(MeCN)₂] with morpholine in refluxing benzene furnishes two compounds, [Re₂(CO)₉(η¹-NC₄H₉O)] (2) and [Re₂(CO)₈(η¹-NC₄H₉O)₂] (3) in 5% and 29% yields, respectively. Reaction of [Re₂(CO)₈(MeCN)₂] with 1-methylimidazole gives [Re₂(CO)₈{η¹-NC₃H₃N(CH₃)}₂] (4) and the mononuclear compound fac-[ReCl(CO)₃{η¹-NC₃H₃N(CH₃)}₂] (5) in 18% and 26% yields, respectively. In the disubstituted compounds 2 and 4, the heterocyclic ligands occupy equatorial coordination sites. The mononuclear compound 5 consists of three CO groups, two N coordinated η¹-1-methylimidazole ligands and a terminal Cl ligand. The XRD structures of complexes 1, 3 and 5 are reported.