Cyclopentadienyl diruthenium metal carbonyl complexes bearing pendant thienyl ligands

Abstract  

Reactions of the thienyl side chain functionalized cyclopentadienyls (C₄H₃S)C(R₁R₂)C₅H₅[R₁, R₂ = CH₃ (1); R₁, R₂ = (CH₂)₅ (2); R₁, R₂ = C₂H₅ (3)] with Ru₃(CO)₁₂ in refluxing xylene gave the corresponding cyclopentadienyl diruthenium carbonyl complexes [(η ⁵-C₄H₃S)CR₁R₂(C₅H₄)Ru(CO)₂]₂ (R₁, R₂ = CH₃ (4); R₁, R₂ = (CH₂)₅ (5); R₁, R₂ = C₂H₅ (6)), which were characterized by elemental analysis, IR and ¹H NMR spectra. The molecular structures of 4, 5 and 6 were determined by single crystal X-ray diffraction.     

Reactions of pyridyl side chain functionalized cyclopentadiene with ruthenium carbonyl

Abstract  

Reactions of the pyridyl side-chain-functionalized cyclopentadiene [C₅H₅CR₂(CH₂C₅H₄N)] [R ₂ = Et₂ (1), (CH₂)₄ (2)] with Ru₃(CO)₁₂ in refluxing xylene gave the new intramolecular C–H activated trinuclear product [μ-(C₅H₃N)CH₂C(C₂H₅)₂(C₅H₄)Ru(CO)]₂Ru(CO)₂ (3) and the normal dinuclear metal complex [(C₅H₄N)CH₂C(CH₂)₄(C₅H₄)Ru(CO)]₂(μ-CO)₂ (4). The structures of the trinuclear complex 3 and dinuclear complex 4 were characterized by elemental analysis, IR spectra, ¹H-NMR and X-ray diffraction.     

Oxidative cross-coupling of some 2,6- and N,N-disubstituted aniline derivatives with 4-aminophenol mediated by cerium(IV) ions in aqueous perchloric acid

Summary The mechanism of the oxidation of mixtures of 2,6-dimethylaniline (1), N,N-dimethylaniline (2), 2,6-diethylaniline (3), N,N-diethylaniline (4), N-methylaniline (5), 2,6-difluoroaniline (6), and 2,3,5,6-tetrafluoroaniline (7) with 4-aminophenol (8) by cerium(IV) ions in aqueous perchloric acid has been investigated. The indoaniline salts [O=C₆H₄=N-C₆H₂(R ¹)₂NH(R ²)₂]⁺ClO ₄ ^– (R ¹=H,R ²=CH₃, C₂H₅ orvice versa) are formed as intermediates in the cross-coupling reaction; they undergo oxidation to imino-4-benzoquinone (9) and its corresponding derivatives by cerium(IV) ions in high yields. The mechanism of this process is discussed.

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Durch Cer(IV)-Ionen induzierte oxidative Kreuzkupplung einiger 2,6- und N,N-disubstituierter Anilinderivate mit 4-Aminophenol in wässriger Perchlorsäure

Zusammenfassung Die Oxidation von Mischungen von 2,6-Dimethylanilin (1), N,N-Dimethylanilin (2), 2,6-Diethylanilin (3), N,N-Diethylanilin (4), N-Methylanilin (5), 2,6-Difluoranolin (6) und 2,3,5,6-Tetrafluoranilin (7) mit 4-Aminophenol (8) durch Cer(IV)-Ionen in wässriger Perchlorsäure wurde untersucht. Als Zwischenprodukte der Kreuzkupplungsreaktion treten die Indoanilinsalze [O=C₆H₄=N-C₆H₂(R ¹)₂NH(R ²)₂]⁺ClO ₄ ^– (R ¹=H,R ²=CH₃, C₂H₅ oder umgekehrt) auf. Diese werden durch Cer(IV)-Ionen in hohen Ausbeuten zu Imino-4-benzochinon (9) und seinen entsprechenden Derivaten oxidiert. Der Mechanismus dieses Vorgangs wird diskutiert.

     

2,6—二乙酰吡啶类双希夫碱配合物的研究——Ⅲ.Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)配合物的合成和表征

制备了由2,6—二乙酰吡啶和肼基硫代甲酸酯衍生的希夫碱C₅H₃N[CH=NNHC(S)XR]₂(X=S,R=CH₃、C₆H₅CH₂;X=O,R=C₆H₅CH₂).离析出类型为MC₅H₃N[CH=NN=C(S)XR]₂(M=Co²⁺、Ni²⁺、Zn²⁺、Pb²⁺和Cd²⁺)的希夫碱配合物.配合物为元素分析、红外、可见—紫外光谱以及磁化率测量所表征.结果指出:上述希夫碱均为N₃S₂型五齿配体.     

Disubstituted diphenyldithiophosphates of cadmium: synthesis,characterization, and single-crystal X-ray structure

A series of new disubstituted diphenyldithiophosphate complexes of cadmium [{(ArO)₂PS₂}₂Cd] (9–12) have been isolated in aqueous media while their donor stabilized adducts [{(ArO)₂PS₂}₂Cd·2C₅H₅N] (13–16) [(Ar = 2,4-(CH₃)₂C₆H₃, 2,5-(CH₃)₂C₆H₃, 3,4-(CH₃)₂C₆H₃ and 3,5-(CH₃)₂C₆H₃)] have been isolated in chloroform. These newly synthesized complexes were characterized by elemental analyses, IR and NMR (¹H, ¹³C and ³¹P) spectroscopic analyses. The dithiophosphate ligands are coordinated bidentate to the cadmium ion via the two thiolate sulfurs. The compounds [{(3,5-CH₃)₂C₆H₃O}₂PS₂HNEt₃] (4) and [{(3,5-CH₃)₂C₆H₃O}₂PS₂]₂Cd(NC₅H₅)₂ (16) crystallize in the monoclinic system with space group P2₁/c. Single-crystal X-ray analysis of 4 reveals that phosphorus of the anion is tetrahedrally bonded to two S and two O atoms. The structure is stabilized by cation–anion N–H?S intermolecular hydrogen bond interactions. In 16, two diphenyldithiophosphate ions are bidentate with both sulfurs coordinated to cadmium. Each forms a four-membered chelate ring in the equatorial plane. Two pyridines are axially coordinated to cadmium leading to octahedral geometry. The thermal properties of this complex have also been examined by combined DTA/DTG thermal analyses.     

Efficient Diastereoselective Synthesis of Chiral Diferrocenylphosphine‐diamines: X‐ray Crystal Structure of [(η5‐C5H5)Fe{(η5‐C5H3)PPh2CH(CH3) N(CH2)2(CH2)2NCH(CH3)PPh2 (η5‐C5H3)}Fe(η5‐C5H5)]

Abstract

Three novel chiral planar diferrocenylphosphine‐diamines 5 (a–c) were designed and synthesized starting with (s)‐(?)‐N,N‐dimethyl‐1‐ferrocenylethylamine‐1 [(S)‐1]. All new compounds were identified by ¹H NMR and MS. The structure of chiral diferrocenylphosphine‐diamine 5c was determined by X‐ray crystallography. Single crystal X‐ray diffraction analysis reveals that the molecular structure of compound 5c [(η⁵‐C₅H₅)Fe{(η⁵‐C₅H₃)PPh₂CH(CH₃) N(CH₂)₂(CH₂)₂NCH(CH₃)PPh₂‐(η⁵‐C₅H₃)}Fe(η⁵‐C₅H₅)] is enantiomerically pure and crystallizes in the noncentrosymmetric P2(1)2(1)2(1) space group; it maintains “Z” shape and contains a piperazine hexahydrate ring bridge. The piperazine ring adopts a favored chair conformation and the chiral center C₂₃ and C₂₉ substituents in S‐configuration.     

Sulfenamides as ligands in transition metal chemistry Pentacarbonyl(Sulfenamide)Chromium(0) Complexes

The complexes Cr(CO)₅(R′SNR₂) [R′ = CH₃; NR₂ = N(CH₃)₂, N(C₄H₈)O. R′ = C₆H₅; NR₂ = N(CH₃)₂, N(C₄H₄)O, N(CH₂? C₆H₅)₂, N(C₆H₁₁)₂] have been prepared by reaction of the sulfenamides with Cr(CO)₅ · THF and characterized by analytical and spectroscopic methods. The IR, ¹H-NMR, UV-VIS, and mass spectra of the complexes support the coordination of the sulfenamide via the sulfur atom. π-acceptor abilities of sulfenamides in the prepared coordination compounds, determined from IR and UV-VIS data, were compared with those of other divalent sulfur conpounds.     

SYNTHESIS OF THE FIRST BENZODISELENAGERMOLES AND ONE SPIROBISDISELENAGERMOLE

Abstract

The first examples of compounds R¹R²GeSe₂C₆H₄R³ (R¹,R²=CH³ C₂H₅, C₃H₂, n-C₄H₉, i-C₅H₁₁, Ph, p-CH₃Ph. R³=H, CH₃, OCH₃) were easily obtained (40–80% yield) from electrophilic cleavage of diselenophenylene zirconocenes by dialkyl or diaryl dichlorogermanes. The synthesis of a spirodi-selenagermole was achieved in the same way using germanium tetrachloride. Analytical data, ¹H and ⁷⁷Se NMR. mass spectra are perfectly consistent with the expected structures.     

Spektroskopische Untersuchungen an Siliciumverbindungen. XXXI. Schwingungsverhalten von p-substituierten N,N-Bistrimethylsilylanilinen

The following p-substituted N,N-bis-trimethlsilyl anilines p-X? C₆H₄? N[Si(CH₃)₃]₂ are prepared by silylation of free amines: X = H, CH₃, C₂H₅, CH₃O, CH₃CO, F, Cl, Br, J, CN, C₆H_S, (CH₃)₃SiO, and [(CH₃)₃Si]₂N, and the isotopic derivatives C₆H₅? ¹⁵N[Si(CH₃)₃]₂ and C₆D₅N[Si(CH₃)₃]₂. The vibrational spectra are reported and assigned. The molecular symmetry of p-[(CH₃)₃Si]₂N? C₆H₄? N[Si(CH₃)₃]₂ is determined. The influence of the mass of the substituents X on the positions of the ν_sSiNSi vibrational frequencies is discussed.     

Synthese von Fluoro-λ5-monophosphazenen und Fluoro-1, 3-diaza-2λ5, 4λ5-diphosphetidinen mittels der Staudinger-Reaktion

Synthesis of Fluoro-λ⁵-monophosphazenes and Fluoro-1,3-diaza-2λ⁵,4λ⁵-diphosphetidines by Means of the Staudinger Reaction 35 Tetrafluoro- and 2 difluorodiaza-diphosphetidines as well as 4 difluoro- and 30 monofluoro-λ⁵-monophosphazenes were prepared by the Staudinger reaction between tervalent phosphorus fluorides, R_nPF_3?n (n = 1, 2; R = R₂N, (CH₂)₅N, O(CH₂)₄N, RO, (CH₂O)₂, alkyl, aryl) and phenylazides, X? C₆H₄N₃ (X = H, 4-CH₃, 4-Cl, 4-Br, 4-NO₂, 3-NO₂). PF₃ does not react with phenylazide The influence of substituents on the structure of the reaction products is discussed. Kinetic measurements allowed to determine the constants λ^P_I of the substituents (CH₂)₅N, O(CH₂)₄N and R(C₆H₅)N (R = CH₃, C₂H₅, n-C₄H₉).     

Heat capacities and densities of mixtures of very polar substances. 3. Mixtures containing either trichloromethane or 1,4-dioxane or diisopropylether

Excess molar heat capacities C _P ^E at constant pressure and excess molar volumes V ^E have been determined, as a function of mole fraction x₁ at 25°C and atmospheric pressure, for 10 binary liquid mixtures containing either trichloromethane (series I) with C₆H₅CH₃, or C₆H₅Cl, or C₅H₅N, or CH₃COCH₃, or C₆H₅NO₂; 1,4-dioxane (series II) with (C₂H₅)₃N, or (CH₃)₂CHOCH(CH₃)₂, or (CH_{3 2}SO); or diisopropyl ether (di-1-methylethyl ether) (series III) with (C₂H₅)₃N, or CHCl₃. The dipole momentsp (10^–30C-m) of the substances range from nearly 0 to 14.1 for nitrobenzene. The C _P ^E of series I and III are all positive, with C _P ^E (x₁=0.5) (J-K^–1-mol^–1) ranging from 1.04 for {x₁CHCl₃+x₂C₆H₅Cl} to 16.66 for {x₁(CH₃)₂CHOCH(CH₃)₂+x₂CHCl₃}. In series II, the C _P ^E are positive and small for {x₁1,4-C₄H₈O₂+x₂(CH₃)₂CHOCH(CH₃)₂}, S-shaped and small for {x₁1,4-C₄H₈O₂+x₂(C₂H₅)₃N}, and negative and small for {x₁1,4-C₄H₈O₂+x₂(CH₃)₂SO}. The excess volumes are small and positive for {x₁CHCl₃+x₂C₆H₅CH₃}, S-shaped for {x₁CHCl₃+x₂CH₃COCH₃}, {x₁1,4-C₄H₈O₂+x₂(C₂H₅)₃N} and {x₁(CH₃)₂CHOCH(CH₃)₂+x₂(C₂H₅)₃N}, and negative for the other systems.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday     

Syntheses,characterization and crystal structures of two square-planar Ni(II) complexes with unsymmetrical tridentate Schiff base ligands and monodentate pseudohalides

Two new square-planar Ni(II) complexes, [NiL¹(NCS)] (1) and [NiL²(N₃)] (2) have been synthesized with the unsymmetrical tridentate Schiff base ligands [(CH₃)₂NCH₂CH₂N=C(CH₃)CH=C(OH)(C₆H₅)], L ¹ H, derived from benzoylacetone and 2-dimethylaminoethylamine and [(CH₃CH₂)₂NCH₂CH₂N=C(CH₃)CH=C(OH)(C₆H₅)], L ² H, derived from benzoylacetone and 2-diethylaminoethylamine, respectively. The complexes have been characterized by elemental analysis, FT-IR, UV-Vis spectroscopy, electrochemical and thermal methods (where applicable). Structures have been established by the single-crystal X-ray diffraction technique which reveals the discrete nature of the complexes in which the metal centers adopt a distorted square planar geometry. Coordination environments of the metal ions in the complexes are satisfied with two different unsymmetrical Schiff base ligands having similar N₂O donor sets and a terminal pseudohalide anion (thiocyanate for 1 and azide for 2).     

Triphenylantimony(v) Derivatives of 2,2-Disubstituted Benzothiazoline Ligands: Synthetic and Spectroscopic Studies

The reactions of triphenylantimony(v) isopropoxide with 2,2-disubstituted benzothiazolines in a 1:2 molar ratio in refluxing benzene solution yielded the corresponding triphenylantimony(v) derivatives (1–5) of the type Ph₃Sb[SC₆H₄N: C(R)CH₂C(O)R']₂, [Where, R═CH₃, R'═CH₃(1); R═CH₃, R'═C₆H₅(2); R═CH₃, R'═4-CH₃C₆H₄(3); R═CH₃, R'═4-ClC₆H₄(4); and R═CF₃, R'═C₆H₅(5)]. All of these newly synthesized derivatives have been characterized by elemental analyses and molecular weight measurements as well as IR and NMR [¹H and ¹³C] spectral studies. On the basis of spectral data, seven-coordination around central antimony atom has been assigned to these derivatives.     

New Cu(II) complexes with polydentate chelating Schiff base ligands: Synthesis, structures, characterisations and biochemical activity studies

We have reported herein the synthesis of three new Cu(II) complexes of tri- and tetradentate Schiff base ligands containing N₃ or N₄ donor set along with terminal NNN⁻ or SCN⁻ ligands: [L¹Cu(NCS)]ClO₄ (1), [L²Cu(NCS)₂] (2) and [L³Cu(NNN)]ClO₄ (3) [L¹ = NC₅H₄C(CH₃)=N(CH₂)₃N=C(CH₃)C₅H₄N, L²= Me₂N–(CH₂)₃–N=C(CH₃)C₅H₄N and L³ = NC₅H₄CH=N–(CH₂)₄–N=CHC₅H₄N]. The complexes have been systematically characterised by elemental, spectroscopic and electrochemical techniques. Antimicrobial activities of the Schiff base ligands and their metal complexes have been studied using the disc diffusion method on the strains of Candida tropicalis and Bacillus megaterium. Structures of all the complexes have been unequivocally established from single crystal X-ray diffraction analyses that show the monomeric units containing a five-coordinated copper center in highly distorted square pyramidal geometry with thiocyanate or azide anion coordinated as terminal ligand. The complexes 1 and 3 crystallise in monoclinic (P2₁/c) and 2 in triclinic (P-1) space group, respectively.     

Synthesis, characterization and the crystal structure of 1-[(N-methyl-N-aryl)amino]ethylferrocenes

The reactions of ferrocenylketimines [(η⁵-C₅H₄CCH₃NAr)Fe(η⁵-C₅H₅)] (Ar=a variety of substituted phenyls) with methyl-iodide in refluxed dichloromethane followed by reduction with sodium borohydride in absolute ethanol led to [(η⁵-C₅H₄CH(CH₃)N(CH₃)Ar)Fe(η⁵-C₅H₅)]. Compound [(η⁵-C₅H₄CH(CH₃)N(CH₃)C₆H₄Cl-p)Fe(η⁵-C₅H₅)] (3d) has been characterized structurally. Compound 3d is monoclinic, space group P2₁/n, with a=8.908(2) Å, b=13.63(1) Å, c=14.510(3) Å and β=107.03°.     

Mass spectrometry of transition metal π-complexes. XV—The effect of substituents on the fragmentation of benchrotrenyls under electron impact

Mass spectra of substituted benchrotrenyls RC₆H₅Cr(CO)₃ where R?H, F, CI, I, CH₃, OCH₃, COOCH₃, C₂H₅, N(CH₃)₂, NH₂, C₆H₅, C(CH₃)₃, p-C₆H₄NH₂, CH₂C₆H₅, CH₂CH₂C₆H₅), 1,3,5-(CH₃)₃C₆H₃Cr(CO)₃ and 1,2,3,5-(CH₃)₄C₆H₂Cr(CO)₃ have been studied. It has been found that for monosubstituted benchrotrenyls there is a linear dependence of the parameter log [Cr]⁺/[RC₆H₅Cr]⁺) on the number of degrees of freedom of the [RC₆H₅Cr]⁺ ion. Decarbonylation of the molecular ions is not affected by the nature of the substituent R. The results are interpreted in terms of the quasi-equilibrium theory of mass spectra.     

Synthesis and characterization of cyclopalladated complexes of benzylamine by IR and NMR spectroscopy studies

The chloro-bridged dimer [Pd(μ-Cl)(C₆H₄CH₂NH₂-κ²-C,N)]₂ reacts with PPh₂Et, P(p-tolyl)₃, AsPh₃, piper (piper =?C₅H₁₀N) and Py in dichloromethane at room temperature for 24 h in a one-to-two molar ratio and undergoing bridge-splitting reactions to give [PdCl(C₆H₄CH₂NH₂–κ²-C,N)L] (L =?PPh₂Et (1a), P(p-tolyl)₃ (1b), AsPh₃ (1c), piper (1d), C₆H₄CH₂NH₂ (3e) and Py (1f)). Complex 1f in THF at room temperature reacts with a stoichiometric amount of TlTfO (thallium triflate, TfO=CF₃SO₃) and Py (molar ratio 1 : 1 : 1) to afford [Pd(C₆H₄CH₂NH₂)(Py)₂]TfO (2). Infrared and NMR spectroscopies allow unambiguous characterization of these products.     

Chemie polyfunktioneller Moleküle, 121. Mitt. Cyclopentadienylruthenium(II)-Komplexe desBis(diphenylphosphanyl)amins und -amids sowie des N,N-Bis(diphenylphosphanyl)-methylamins und -ethylamins

Summary This synthetic and structural work describes a series of half-sandwich cyclopentadienylruthenium(II) complexes containing the diphosphazane ligands [(C₆H₅)₂P]₂NR (R=H:Hdppa,1a;R=CH₃:dppma,1b;R=C₂H₅:dppea,1c;R=Li:Lidppa,1d). Treatment of1a, d with CpRuCl(PPh₃)₂ (Cp=⁵-C₅H₅, Ph=C₆H₅,2) in a molar ratio of 1:1 in boiling aromatic hydrocarbons affords the neutral complexes CpRuCl(Hdppa) (3) and CpRu(dppa)PPh₃ (6). The ionic complexes [CpRu(Ph₂P-NR-(PPh₂)PPh₃)Cl (R=CH₃:4a;R=C₂H₅:4b) are formed by the reaction of1b,c with2. One pot reactions of1a–c with2 in the presence of NH₄PF₆ in boiling CH₃OH give only the ionic compounds [CpRu(Ph₂P-NR-PPh₂)(PPh₃)]PF₆ (R=H, CH₃, C₂H₅;5a–c). The sulfur dioxide and hydride complexes [CpRu(Hdppa)¹-SO₂]Cl (7) and CpRu(H)Hdppa (8) are obtained by the interaction of3 with SO₂ or NaOCH₃. All compounds are characterized as far as possible by IR, Raman,³¹P{¹H} NMR,¹H NMR,¹³C{¹H} NMR, FD mass spectra, and their conductivity in CH₂Cl₂ solution. The X-ray crystal structures of3 and5a reveal that the P(1)-N(1)-P(2) angle of the coordinated ligand1a in both complexes is reduced to about 100° in comparison to free uncoordinated1a (119°). This small angle leads to a short P(1)–P(2) bond distance of 259.4 pm in3 and 254.3 pm in5a. The molecules of3 are connected by intermolecular (NH...Cl) hydrogen bridging bonds forming chains along thez axis of the unit cell. The crystals of5a contain two independent pairs of ions in the unit cell (Z=8). In5a no hydrogen bonds exist between the NH-groups and the PF ₆ ^– anions.

     

Triphenyltelluroniumcarbamate und -dithiocarbamate

Triphenyltelluronium Carbamates and Dithiocarbamates Compounds of the type (C₆H₅)₃TeS₂CNR₂ with R ? CH₃, i-C₃H₇, C₆H₅ and (C₆H₅)₃TeO₂CN(CH₃)₂ are obtained by reaction of triphenyltelluronium chloride with sodium dithiocarbamates or ammonium carbamate. In the same way ethylene- bis(N,N′-methyldithiocarbamicacid-S,S′-λ⁴-triphenyltellurylester) was synthesized. (C₆H₅)₃TeO₂CN(CH₃)₂ reacts with CS₂ to give (C₆H₅)₃TeS₂CN(CH₃)₂.     

Synthesis,structural characterization,and in vitro antimicrobial properties of salicylate and pyrazoline complexes of bismuth(III)

Displacement reactions of dichlorobismuth(III)pyrazolinates with oxygen donors such as sodium salicylate and acetate in 1?:?1 and 1?:?2 molar ratio in refluxing anhydrous benzene yields (C₁₂H₁₅N₂OX)Bi(C₆H₄O₃), (CH₃COO)BiCl(C₁₅H₁₂N₂OX), and (CH₃COO)₂Bi(C₁₅H₁₂N₂OX) [C₁₂H₁₅N₂OX?=?3(2′-hydroxyphenyl)-5-(4-X-substituted phenyl) pyrazoline X?=?H in 1,5,9, CH₃ in 2,6,10, OCH₃ in 3,7,11, and Cl in 4,8,12, respectively, (C₆H₄O₃)?=?salicylate and (CH₃COO)?=?acetate]. Newly synthesized derivatives are brown solids, soluble in organic solvents like benzene, chloroform, and acetone. The compounds have been characterized by elemental analyses (C, H, N, Cl, and Bi), molecular weight measurements, and spectral (IR, ¹H NMR, ¹³C NMR) studies. The (C₁₂H₁₅N₂OX) and (C₆H₄O₃) are bidentate while (CH₃COO) is monodentate to bismuth(III), leading to a distorted trigonal bipyramidal structure. The complexes were screened against different bacteria and fungi showing potential antibacterial and antifungal activities.