Reaction of tricarbonyl[(1-4-η)-2-methoxy-5-vinylidene-cyclohexa-1,3-diene]iron derivatives with carbene: (2+1) cycloaddition for the rapid synthesis of spiro[2,5]octane

Tricarbonyl[(1-4-η)-2-methoxy-5-methylene-cyclohexa-1,3-diene]iron (1a) and tricarbonyl[(1-4-η)-2-methoxy-5-isopropylene-cyclohexa-1,3-diene]iron (1b) complexes are unstable 4-vinylidene cyclohexanone equivalents and these react regio- and stereoselectively with carbenes and metallocarbenes to give spiro[2,5]octane ring system. The (2+1) cycloaddition reaction provides a rapid entry into spiro[2,5]octane ring system. In cases where the carbene and metallocarbene contain a good bulky leaving group or an electron-withdrawing group, the cyclopropane ring-opening products are obtained.     

[2+4] Cycloaddition of η6-(styrene)chromium tricarbonyl and conjugated dienes

Cycloaddition of η⁶-(styrene)chromium tricarbonyl to hexa-2,4-diene or cyclopentadiene afford the Diels-Alder adducts with retention of the Cr(CO)₃ group, whereas cyclohexa-1,3-diene undergoes aromatization to give η⁶-(benzene)chromium tricarbonyl. The counter synthesis of these (arene)chromium tricarbonyl derivatives from uncoordinated adducts of the Diels-Alder reaction and chromium hexacarbonyl was carried out.     

(Tetragermacyclobutadiene)ruthenium tricarbonyl [η4-(But 2MeSi)4Ge4]Ru(CO)3

Tetrakis(di-tert-butylmethylsilyl)tetragermacyclobutadiene]ruthenium tricarbonyl [η⁴-(Bu^t ₂MeSi)₄Ge₄]Ru(CO)₃ is synthesized. This analogue of well-known cyclobutadiene transition metal complexes bears a tetragermacyclobutadiene derivative as ligand. The structure and spectroscopic parameters of the complex are compared with those of its iron-containing analogue [η⁴-(Bu^t ₂MeSi)₄Ge₄]Fe(CO)₃. Based on experimental data and results of quantum chemical calculations, it is shown that the π-donating ability of ligands increases upon replacement of carbon atoms in the cyclobutadiene moiety by silicon or germanium atoms, tetrasilacyclobutadiene and tetragermacyclobutadiene being comparable in π-donating activity.     

Phenyl directing groups in the demethoxylation route to tricarbonyl(η5-cyclohexadienyl)iron(1 +) complexes

Acid catalysed demethoxylation of tricarbonyl(η⁴-2-methoxy-6-phenyl-1,3- cyclohexadiene)iron(0) leads to the exclusive formation of a 3-phenyl salt, rather than the product of minimum rearrangement, a 1-phenyl salt. With an additional 2-methyl substituent present, the competing directing influence is overcome by the phenyl group. The importance of the phenyl substituent in promoting regioselectivity is demonstrated by the demethoxylation of a 2,5-dimethyl-3-methoxy substituted complex, which led to a mixture of products.     

Nucleophilic substitution reactions of acetylides on substituted tricarbonyl(η6-fluoroarene)chromium and reactions of tricarbonyl[η6-(2-trimethylsilylethynyl)toluene]chromium and tricarbonyl[η6-(p-ethynyl-phenylethynyl)benzene]chromium with dicobalt octacarbonyl

Nucleophilic substitution reactions of various acetylides on substituted tricarbonyl(η⁶-fluoroarene)chromiums were pursued. The reaction presumably underwent a more complicated mechanism rather than the direct substitution on the fluorine-bearing carbon. The organometallic compounds (η⁶-C₆H₃R¹R²R³)Cr(CO)₃ (R¹: CC–C₆H₄CH₃, R²: o-Me, R³: H (5a), R¹: CC–C₆H₄CH₃, R²: o-OMe, R³: H (6a), R¹: CC–C₆H₄CH₃, R²: m-OMe, R³: H (6b), R¹: CCPh, R²: o-Me, R³: o-OMe (8b), R¹: CCPh, R²: m-Me, R³: m-OMe (8c), R¹: CCSiMe₃, R²: o-Me, R³: H (9a), R¹: CC–C₆H₄CCH, R²: H, R³: H (12), R¹: CC–C₆H₄CCH, R²: o-Me, R³: H (13)) as well as the organometallic dimmer [{(η⁶-o-Me-C₆H₄)Cr(CO)₃(di-ethynyl)] (di-ethynyl: CC–C₆H₄CC (14)) have been synthesized from nucleophilic substitution reactions of tricarbonyl(η⁶-fluoroarene)(chromium) compounds with suitable acetylides. The products have been characterized by spectroscopic means. In addition, (8b) and (8c) were characterized by X-ray diffraction studies. Further reactions of (9a) and (12) with appropriate amount of Co₂(CO)₈ yielded μ-alkyne bridged bimetallic complexes, Co₂(CO)₆{μ-Me₃SiCC–(o-tolueneCr(CO)₃} (10) and (Co₂(CO)₆)₂{μ-HCC–C₆H₄–CC–(benzene)Cr(CO)₃)}(15), respectively. Both (10) and (15) were characterized by spectroscopic means as well as single crystal X-ray crystallography. The core of these molecules is quasi-tetrahedron containing a Co₂C₂ unit. A two-dicobalt-fragments coordinated di-enyls complex, (Co₂(CO)₆)₂{μ-HCC–C₆H₄–CC–H} (17), was synthesized from the reaction of 1,3-diethynylbenzene with Co₂(CO)₈. Crystallographic studies of (17) also show that it exhibits a distorted Co₂C₂ quasi-tetrahedral geometry.     

Self-recognition by the iron chiral auxiliary [(η5-C5H5)Fe(CO)(PPh3] in the formation of (RR,SS)-[(η5-C5H5)FE(CO)(PPh3)COCH2]2CH2

Complete self-recognition of chirality is observed in the Michael addition of the enolate derived from R,S-[η⁵-C₅H₅Fe(CO)(PPh₃-COCH₃] to the acryloyl complex R,S-[(η⁵-C₅H₅Fe(CO)(PPh₃)-COCHCH₂)] to generate exclusively the single diastereoisomer of the glutaroyl complex RR,SS-[(η⁵-C₅H₅)Fe(CO)(PPh₃)COCH₂]₂CH₂.     

Some reactions of [(η6-C6Me6)Ru(η6-[2.2]paracyclophane)]-[BF4]2 with nucleophiles

Single addition of the nucleophiles X⁻ (X = H, CN, OH) to the less sterically hindered ring in [(η⁶-C₆Me₆)Ru(η⁶-C₁₆H₁₆)][BF₄]₂ (1) proceeds smoothly to produce, as the sole product, [(exo-η⁵-C₆Me₆X)Ru(η⁶-C₁₆H₁₆)][BF₄]. Use of Na[BD₄] in place of Na[BH₄] gives the expected shift in ν(C-H_exo) in the infrared spectrum.     

Synthesis and structure of tetra-p-tolylantimony complexes [(4-MeC6H4)4Sb] 2 + [Hg2I6]2−, [(4-MeC6H4)4Sb] 2 + [HgI4]2−, [(4-MeC6H4)4Sb] 3 + [Sb3I12]2−, and [(4-MeC6H4)4Sb]+[ReO4]−

Complexes [(4-MeC₆H₄)₄Sb] ₂ ⁺ [Hg₂I₆]^2? (I), [(4-MeC₆H₄)₄Sb] ₂ ⁺ [HgI₄]^2? (II), [(4-MeC₆H₄)₄Sb] ₃ ⁺ [Sb₃I₁₂]^2? (III), were synthesized by reactions of tetra-p-tolylantimony iodide with mercury iodide and antimony iodide, respectively. Tetra-p-tolylantimony perrhenate [(4-MeC₆H₄)₄Sb]⁺[ReO₄]^? (IV) was prepared from tetra-p-tolylantimony chloride and sodium perrhenate in acetone. Crystal structures of complexes I, II, and IV were determined by X-ray crystallography. Mercury and rhenium atoms have tetrahedral coordinations in these complexes. The Hg-I and Re-O distances in the structures of I, II, and IV vary within 2.7719(13)–2.7908(12)Å, 2.7028(3)–2.9163(3) Å, and 1.693(3)–1.744(3) Å, respectively. Antimony atoms in two crystallographically independent trinuclear centrosymmetric [Sb₃I₁₂]^2? anions of complex III have an octahedral environment. Each terminal SbI₃ fragment (Sb-I_t, 2.8265(9)–2.8333(10)Å) is bound to the central atom through tree bridging iodine atoms (Sb(2)-I_br, 3.2275(9)–3.3620(10)Å). The distances between the central Sb atom and bridging iodine atoms are much shorter (Sb(1)-I_br, 3.0153(6)–3.0316(6) Å; Sb(3)-I_br, 2.9926(6)–3.0074(6) Å).     

A chemical oscillating reaction in NaBrO_3-pyruvic acid-H_2SO_4-[Ni(Me_2[14]1,3-diene N_4)]~(2+) system

In this paper we report a chemical oscillation catalyzed by [Ni(Me2[14]1,3-diene N4)]2+ (Me2[14]l,3-diene N4 denotes 2,3-dimethyl-l,4,8,ll-tetraazacyclotetradeca-1,3-diene) in BrO3--pyruvic acid-H2SO4 system.The domain of the existence of the oscillation was obtained.The effects of initial concentration of the components on the oscillation were studied.The features of the oscillations were described in detail.We also examined the effects of Ag+,Hg2+,CCl4,free radical inhibitors,etc.on the osillations.     

New one-pot methods for the synthesis of metallonium dications [1,2-(η5:σ:σ-C5Me3(CH2)2)(η5-Cp*)Os]2+ and [1,1"-(η5:σ-C5Me4CH2)2Os]2+ based on decamethylosmocene or its derivatives

The reaction of Cp*₂Os or [Cp*₂OsH]⁺PF₆ ^– with oleum on heating or UV photolysis of Cp*₂Os in oleum under an inert atmosphere afforded two metallonium dications, viz., [1,2-(⁵::-C₅Me₃(CH₂)₂)(⁵-Cp*)Os]²⁺ and [1,1"-(⁵:-C₅Me₄CH₂)₂Os]²⁺. The structures of these dications were confirmed by the results of their alkoxylation. The [Os(H)₂(Cp*)₂]²⁺ and [Os(H)(Cp*)(C₅Me₄CH₂)]²⁺ dications were detected as intermediates in the above syntheses. All compounds were characterized by NMR spectroscopy. Calculations of the dications were carried out using the density functional theory (DFT).     

Synthesis and Crystal Structure of [(η~5-C_5H_5)(THF)Sm]_2[μ-η_2:η_2-N_2Ph_2]_2·2THF

1 INTRODUCTION Since last decade, the chemistry of divalent organolanthanide complexes has yielded particularly remarkable and striking results. The major break- through in the chemistry of divalent organolan- thanides, especially Sm(II), includes the u…     

Design of (2Z)-2-cyano-2-[2-[(E)-2-[5-[(E)-2-(4-dimethylaminophenyl)vinyl]-2-thienyl]vinyl]pyran-4-ylidene]acetic acid derivatives as D-π-A dye sensitizers in molecular photovoltaics: a density functional theory approach

Research on Chemical Intermediates - The use of computational methods such as density functional theory (DFT) in material design has attracted considerable attention aimed at achieving efficient...     

[4 + 6]-cycloaddition von 1,3-butadien an hexacarbonyl-μ-η6:6-heptafulvalen-dichrom(0)

The thermal reaction of heptafulvalene (I) with [Cr(CO)₃(CH₃CH)₃] (II) gives the hexacarbonyl-η^6:6-heptafulvalenedichromium(0) complex (III). UV irradiation of complex III in THF solution, with 1,3-butadiene (IV) in successive [4 + 6]-cycloadditions and decomplexations gives the complexes tricarbonyl-η⁶-11-(2,4,6-cycloheptatrien-1-ylidene)bicyclo[4.4.1]undeca-2,4,8-trine-chromium(0) (V) and tricarbonyl-η⁶-bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene)-chromium(0) (VI). On warming, VI looses the bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene) hydrocarbon ligand (VII). The reaction of VII with [Mo(CO)₃(diglyme)] (VIII) gives the tricarbonyl-η⁶-bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene)molybdenum(0) complex (IX). The compounds III, V–VII and IX were characterized by IR and NMR spectra (¹H, ¹³C) and by C,H elemental analysis.     

Structural chemistry of titanium and aluminium bimetallic hydride complexes VI. Molecular structure and physico-chemical properties of (η5-C5 H5) 2Ti(μ2-H)2 Al(Cl) (μ2 -H)2Ti(η5-C5H 5)2, a catalyst-precursor for hydrogenation in the [(η5-C5H5)2TiCl]2-LiAIH4 system

The complex (Cp₂Ti)₂AlH₄Cl has been isolated from the catalytic system (Cp₂TiCl)₂-LiAlH₄, which is a precursor of the catalyst for the hydrogenation and isomerization of olefins. This complex has been studied by X-ray diffraction. The complex forms rhomboidal crystals with unit cell dimensions a = 10.414, b = 11.998, c = 16.008 Å, space group P2₁2₁2₁, Z = 4, and density ϱ_calc = 1.40 g/cm³. The Cp₂Ti moieties are linked to the Al atom via double hydrogen bridges; the Cl atom is bonded to the Al atom. Analysis of the EPR spectral data and some chemical properties of (Cp₂Ti)₂AlH₄Cl solutions has led us to suggest a mechanism for the formation of the catalytically active species upon interaction of this compound with olefins and solvating solvents.     

Synthesis of 4′-[3-methyl-5-thioxo-1H-1,2,4-triazol-4(5H)-yl]-2′,5′-diphenyl-2′,4′-dihydro spiro[indolin-3,3′[1,2,4]triazol]-2-one derivatives

In this paper 1,3-dipolar cycloaddition reaction has been studied. An efficient synthesis of 4′-[3-methyl-5-thioxo-1H-1,2,4-triazol-4(5H)-yl]-2′,5′-diphenyl-2′,4′-dihydro spiro(indolin-3,3′[1,2,4]triazol)-2-one derivatives using triethylamine in MeCN at room temperature is reported. The structures of the obtained compounds were confirmed by means of elemental analysis, MS and spectral (IR, ¹H, and ¹³C NMR) methods.     

2-[2′-(6′-Methyl-benzothiazolyl)azo]-5-dimethylaminobenzoic acid as a new reagent for rapid spectrophotometric determination of copper

2-[2-(6-methyl-benzothiazolyl)azo]-5-dimethylaminobenzoic acid (MBTAMB) has been synthesized and employed as a new reagent for the spectrophotometric determination of copper(II). A blue complex is formed from MBTAMB and Cu(II) in the range of pH 2.0–5.0 in aqueous ethanol. The composition of the complex is Cu(II) MBTAMB=1 1. The maximum absorption of the complex is at 660 nm, its apparent molar absorptivity is 7.0 × 10⁴ 1· mole^–1 · cm^–1. Beer's law is obeyed for copper in the range of 0–0.72 g/ml. The method has been used for the determination of micro amounts of copper in aluminium alloy. The proposed method is simple, rapid and accurate.     

Evolution of Routes for Asymmetric Total Synthesis of Cyclocitrinol Enabled by Type Ⅱ [5+2] Cycloaddition

Main observation and conclusion The asymmetric total synthesis of an unusual C25 steroid containing a unique bicyclo[4.4.1]undecene A/B ring system,resulting in...     

On the isomerization of cyclooctyne into cycloocta-1,3-diene: synthesis, characterization and structure of a dinuclear platinum(II) complex with a μ-η2:η2-1,3-COD ligand

The Zeise's salt type cyclooctyne compound [K(18C6)][PtCl(3)(COC)] (1; COC = cyclooctyne; 18C6 = 18-crown-6) was found to react in chloroform solution at room temperature within several weeks yielding the dinuclear cyclooctadiene compound [K(18C6)](2)[(PtCl(3))(2)(μ-η(2):η(2)-1,3-COD)] (2; 1,3-COD = cycloocta-1,3-diene) and non-coordinated cycloocta-1,3-diene. The identity of 2 was confirmed by microanalysis, NMR spectroscopy ((1)H, (13)C) and electrospray ionization mass spectrometry (ESI-MS). A single-crystal X-ray diffraction analysis of 2 exhibited a bridging μ-η(2):η(2)-cycloocta-1,3-diene ligand with non-conjugated double bonds each coordinated to a PtCl(3) fragment. On the basis of DFT calculations as well as energy decomposition analyses (EDA), charge decomposition analyses (CDA) and natural bond orbital (NBO) analyses the peculiarities of the nature of the Pt-C bonds in the dinuclear complex anion [(PtCl(3))(2)(μ-η(2):η(2)-1,3-COD)](2-) (2a') compared with those in mononuclear olefin complexes of Zeise's salt type [PtCl(3)L](-) (L = η(2)-1,3-COD, 3a'; cis-but-2-ene, 4a'; COE, 5a'; COE = cyclooctene) are discussed. Furthermore, the driving force for the strongly exergonic reaction with formation of the cyclooctadiene complex 2a' was found to be a significant release of ring strain of the cyclooctyne ligand in the starting compound 1.     

Synthesis and Structural Characterization of [(η~5-C_5Me_5)_2Mo_2Fe_2S_4Br_2]

1 INTRODUCTION We once reported a CS bond cleavage reaction of (h5-C5Me5)Mo(StBu)3, which led to a Mo(IV) thio/thiolate complex (h5-C5Me5)MoS2(StBu)[1]. This reaction was facilitated by oxidants such as S8, gray selenium, and FeCl3[2]. The reaction with FeCl3 gave rise to a cubane cluster [(h5-C5Me5)2Mo2Fe2S4Cl2], which served as an excellent building block to construct various Mo/Fe/S clusters[2]. In this paper, we report the crystal structure of [(h5-C5Me5)2Mo2Fe…