Reaction of mercury halides of cyclopentadienyl derivatives of manganese and rhenium carbonyls with triphenylphosphine complex of platinum(0)

Conclusions It was discovered that the mercury halides of the cyclopentadienyl derivatives of manganese and rhenium carbonyls react with tris(triphenylphosphine)platinum to give new complexes with a platnium-carbon -bond.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1894–1896, August, 1977.     

Phenyltellurolate-bridged heterometallic complexes combining rhenium tricarbonyl with (dicarbonyl)(cyclopentadienyl)iron or bis(diphenylphosphino)ethaneplatinum

A reaction of CpFe(CO)₂TePh with Re(CO)₃(THF)₂Cl in THF gave the heterometallic complex [CpFe(CO)₂(μ-TePh)]₂Re(CO)₃Cl (I). Either iron atom in complex I is linked to rhenium by only one Phenyltellurolate bridge. When treated with (Dppe)Pt(TePh)₂, complex I underwent transmetalation by elimination of two CpFe(CO)₂TePh molecules followed by the formation of the heterometallic chelate complex (Dppe)Pt(μ-TePh)₂Re(CO)₃Cl (II). Complex II was also obtained in an independent way from (Dppe)Pt(TePh)₂ and Re(CO)₃(THF)₂. Structures I and II (II · MePh and II · CDCl₃) were identified by X-ray diffraction (CIF file, CCDC nos. 981467, 981468, and 981469, respectively).     

Three compounds from the reaction between dicarbonyl(methylcyclopentadienyl)(tetrahydrofuran)-manganese and 4-cyanopyridine

The isolation and characterization of two mononuclear complexes and one binuclear compound from the reaction between dicarbonyl(methylcyclopentadienyl) (tetrahydrofuran)manganese and 4-cyanopyridine are reported. The competition between the pyridine and nitrile nitrogen centers for coordination with the (η⁵ -C₅H₄CH₃)Mn(CO)₂ fragment results in the formation of two mononuclear complexes, of which the N¹ -coordinated isomer is more stable.     

Mercury derivatives of manganese cyclopentadienyl and methylcyclopentadienyltricarbonyl

Summary Manganese cyclopentadienyl and methylcyclopentadienyltricarbonyl are mercurated just as readily as ferrocene and benzene by mercuric acetate in alcoholic solution, forming mono and dimercurated products.     

双(环戊二烯基)二羰基钛、双(甲基环戊二烯基)二羰基钛和卤代烃的反应

通过双(甲基环戊二烯基)二羰基钛、双(环戊二烯基)二羰基钛与卤代烃的反应合成了33个相应的酰基卤化钛,其中31个未见文献报道.研究了不同卤代烃与这些二羰基茂钛化合物反应的特点.顺磁共振法显示反应都经过自由基中间体,提出了羰基插入RX和R基偶联反应历程的初步结论.     

二羰基[三-(三甲硅基)]环戊二烯基铁卤化物的合成及结构

三-(三甲硅基)环戊二烯与五羰基铁在二甲苯中回流6h, 反应停留在生成η^5-[ (Me~3Si)~3C~5H~2]Fe(CO)~2H(1) 的中间阶段, 这是由于茂环上有三个大位阻取代基(Me~3Si)的存在阻止了1进一步反应成双核Fe-Fe键化合物. 1分别与CHCl~3·NBS及I~2反应, 生成相应的铁卤化物, η^5-[1,2,4-(Me~3Si)~3C~5H~2]Fe(CO)~2X (X: Cl, 2; Br, 3; I, 4).测定了2 的晶体结构.     

Oxidation of magnesium with cyclopentadienyl(triphenylphosphine)nickel chloride in aprotic solvents

The products of magnesium oxidation with cyclopentadienyl(triphenylphosphine)nickel chloride were revealed. Effective equilibrium constants of adsorption of the reagents on the metal surface, entropy and enthalpy of these processes, rate constants, and activation energy were determined. A probable scheme of the process is assumed.     

Triphenyl phosphine complex of cyclopentadienyl(manganese dicarbonyl triphenyl phosphine) gold

Conclusions The triphenyl phosphine complex of cyclopentadienyl (manganese dicarbonyl triphenyl phosphine) gold was obtained.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2641–2642, November, 1973.     

Synthesis of σ-platinum cyclopentadienyl derivatives of manganese and rhenium carbonyl compounds

Russian Chemical Bulletin -     

Synthesis and structural characterization of acetatobis(triphenylphosphine)dicarbonylrhenium(I). new car☐ylato derivatives of rhenium(I)

Acetatobis(triphenylphosphine)dicarbonylrhenium (I), (PPh₃)₂(CO)₂Re(O₂CCH₃), has been prepared in a novel way by treating (PPh₃)₂(CO)₂Re(NHCOR) (R = C₆H₅, p-MeC₆H₄) with triethylamine and water in the presence of air. Oxidation of the ethyl group of the tertiary amine is presumably involved in the formation of the acetate ligand. Three-dimensional single-crystal X-ray diffraction analysis shows that the complex is octahedral with the phosphines in trans positions and the acetate ion acting as a chelating ligand. The complex crystallizes in theP2₁/c space group with cell dimensions a = 17.63(2), b = 9.72(1), c = 20.95(2)Å, β = 104°38'(6'), Z = 4. The mean values of bond lengths observed are Re-P 2.415, Re-O 2.21 and Re-(CO) 1.85Å. The same acetate derivative and a series of car?ylato complexes (PPh₃)₂(CO)₂Re(O₂CR') have been obtained from reactions of Re(CO)₂(PPh₃)₃H with car?ylic acids R'COOH (R' = H, CH₃, CH₂Cl, CH₂CH₃, C₆H₅). When trifluoroacetic acid is used, a product of formula (PPh₃)₂(CO)₃Re(OC(O)CF₃) is isolated. The action of neutral ligands L on some of these products gave rise to derivatives of formula (PPh₃)₂(CO)₂(L)Re(OC(O)R') (L = CO, R' = H, CH₃, C₆H₅; L = pMeC₆H₄NC, R' = CH₃), having monodentate car?ylato moieties.     

Synthesis and characterization of thiosemicarbazone derivatives of 2-ethoxy-3-methoxy-benzaldehyde and their rhenium(I) complexes

The ligands (HL¹, HL² and HL³) have been prepared and their reaction with fac-[ReX(CO)₃(CH₃CN)₂] (X = Br, Cl) in chloroform gave the adducts [ReX(CO)₃(HL)] (1a X = Cl, R = H; 1a′ X = Br, R = H; 1b X = Cl, R = CH₃; 1b′ X = Br, R = CH₃; 1c X = Cl, R = Ph; 1c′ X = Br, R = Ph) in good yield. All the compounds have been characterized by elemental analysis, mass spectrometry (FAB), IR and ¹H NMR spectroscopic methods, and the structures of the ligands have been elucidated by X-ray diffraction. In the case of HL¹, we have tried the reaction with [ReX(CO)₅] (X = Br, Cl) in toluene and we proved the formation of the adduct also by this way by the isolation of single crystals of 1a′ · ½C₇H_8.     

Novel cyclometallated Pd(II) and Pt(II) complexes with indole derivatives and their use as catalysts in Heck reaction

Several palladacycle and platinacycle complexes have been prepared from easily available or naturally occurring indole derivatives, such as gramine and related compounds. Dimeric complexes were obtained with Pd(OAc)₂, while Pt(DMSO)₂Cl₂ mainly afforded monomeric structures. A notable feature of these reactions was the formation of new M-C bonds between Pd or Pt and C-2 and C-3 of the indole ring. With ligands like 2-(2′-pyridyl)-1H-indoles, N-N metallacycles were generated instead: in fact new C-M bonds with the C-3 position could only form if N-substituted indoles were used. The reactivity of Pd dimeric complexes with PPh₃, sym-collidine and DMAP was explored to obtain monomeric complexes. Three such compounds were prepared, one of which was characterized by X-ray diffraction. Metathetical reactions were carried out to effect a ligand exchange replacing OAc with halide ions, with the aim to synthesize μ-Cl and μ-Br bridged structures. Turning to the synthesis of hetaryl complexes, functionalization of the C-2 position on the indole ring was achieved. These complexes were prepared by substitution reactions starting from gramine and/or its alkylammonium salts.