Redox-induced η5 ⇔ η3 haptotropy of the fluorenyl ligand in 9-substituted η5-fluorenylmanganesetricarbonyl complexes

It has been shown by cyclic voltammetry in THF within the –90 to 40 °C temperature range that fluorenyl (⁵-9-R-C₁₃H₈)Mn(CO)₃ complexes (R=Bu^t (3) and Ph (4)) undergo two-electron reduction to form allyl type [(³-9-R-C₁₃H₈)Mn(CO)₃]^2– dianions as final products. At low temperatures complexes3 and4 are reduced in two one-electron steps according to the EEC-scheme. The first step is reversible and corresponds to the formation of 19-radical anions 3^–. and 4^–.. TheE ⁰ values for redox pairs3 ^0/–. and4 ^0/–. are –1.88 and –1.73 V, respectively. The further reduction of radical anions3 ^–. and4 ^–. at more negative potentials is accompanied by fast ^{5 3} haptocoordination of the fluorenyl ligand to form 18-dianions [(³-9-R-C₁₃H₈)Mn(CO)₃]^2–. These dianions obtained by the reduction of complexes3 and4 by the radical anion of pyrene are stable at –80 °C and are characterized by their IR spectra. At room temperature the ^{5 3} hapticity change is a fast and reversible process occurring at the step of 19-radical anions3 ^–. and4 ^–. and leading to the electron deficient 17-species [(³-9-R-C₁₃H₈)Mn(CO)₃]^–., which are reduced easier than the initial complexes. As a result, complexes3 and4 are reduced to the corresponding dianions [(³-9-R-C₁₃H₈)Mn(CO)₃]^2– at room temperature in one reversible two-electron step according to the ECE-scheme. Reactivities of 19e^–-species of the isomeric ⁵- and ⁶-fluorenylmanganesetricarbonyl complexes are compared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1347–1353, July, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-05209) and the International Science Foundation (Grant No. REV 000).     

Oxidation of isomeric η6- and η5-fluorenylchromiumtricarbonyl anions

The oxidation of the carbon-centered [(⁶-C₁₃H₉)Cr(CO)₃]^– anion (1 ^–) results in formation of (-⁶:⁶-9,9-bifluorenyl)bis-chromiumtricarbonyl (3) due to coupling of the intermediate carbon-centered radical (1^.). The oxidation of the metal-centered anion [(⁵-C₁₃H₉)Cr(CO)₃]^– (2 ^–), which is isomeric to the 1^– anion, gives an equilibrium mixture of the chromium-centered radical {(⁵-C₁₃H₉)Cr(CO)₃}^. (2 ^.) and its dimer [(⁵-C₁₃H₉)Cr(CO)₃]₂ (6). Radical2 ^. readily reacts with MeI and the solvent (THF); the resulting derivatives, (⁵-C₁₃H₉)Cr(CO)₃R (R=Me (10); R=H (7)), undergo fast ricochet inter-ring ⁵⁶ rearrangements into (⁶-9R-C₁₃H₉)Cr(CO)₃ (R=CH₃ (9); R=H (4)).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1354–1358, July, 1995.The authors are grateful to D. V. Zagorevskii who recorded the mass spectra. This study was financially supported by the Russian Foundation for Basic Research (Grant No. 94-03-05209) and the International Science Foundation (Grant Nos. MQ 4000 and REV 000).     

Acyclic boron-containing π-ligand complexes: η2- and η3-coordination modes

Cyclic boron-containing π-ligands such as boratabenzenes and borollides are well established, in particular as supporting ligands. By contrast, the chemistry of acyclic boron-containing π-ligands has remained relatively unexplored, presumably in part due to the higher reactivity of acyclic π-ligands relative to cyclic analogues. This perspective is focused on the synthesis, structures and reactivity of isolated transition metal complexes bearing η(n)-coordinated (n = 2 or 3) acyclic boron-containing ligands. Both monometallic and multimetallic compounds are included, and are discussed with an emphasis on metal-ligand and intraligand bonding and parallels with hydrocarbon π-ligand complexes.     

The interconversion of η5 and η3 hapticities in cycloheptadienyl complexes of molybdenum and tungsten

[Mo(CO)₄(η⁵-C₇H₉)]⁺ (1) reacts with acetonitrile to give [Mo(CO)₂(NCMe)₃(η³-C₇H₉)]⁺ (3), which is precursor of a wide reange of η⁵-cycloheptadienyl complexes [Mo(CO)₂L₂(η⁵-C₇H₉)]⁺ [6, L = PPH₃; 7, L₂ = Ph₂PCH₂PPh₂; 8, L₂ = 1,3-cyclohexadiene; 9, L₂ = 2,2′-dipyridyl]; 9 reacts reversibly with NCMe to give [Mo(CO)₂(NCMe)(dipy)(η³-C₇H₉)]⁺ (10).     

Ortho-metallation of η-pyrrolylmetal complexes with triosmium clusters

The cluster [O₃(CO)₁₀(MeCN)₂] reacts with (η-cyclopentadienyl)(η-pyrrolyl)iron [azaferrocene, Fe(C₅H₅)(C₄H₄N) under mild conditions to give the oxidative addition product [Os₃H{(C₄H₃N)Fe(C₅H₅)}(CO)₁₀]. The group (C₄H₃N)Fe(C₅H₅) acts as a three-electron donor through the ortho-metallated pyrrolyl ring. An analogous compounds, [Os₃H{(C₄H₃N)Mn(CO)₃}(CO)₁₀], is obtained by the reaction of [Os₃(CO)₁₀(MeCN)₂] with [Mn(η-pyrrolyl)(CO)₃].     

The reaction of N-phenyldialkynylimines with η5-cyclopentadienyldicarbonylcobalt

N-Substituted dialkynylimines react with η⁵-cyclopentadienyldicarbonylcobalt to give a mixture of η⁴-cyclobutadiene cobalt complexes, the structures of which have been determined by X-ray crystallography.     

Synthesis of a bridging-imido η-cycloheptatrienyl molybdenum complex

Treatment of [(η-C₇H₇)Mo(μ-Cl)₃Mo(η-C₇H₇)] (1) with ArNHLi (Ar = 2,6-diisopropylphenyl) gives the bridging-imido binuclear compound [(η-C₇H₇)Mo(μ-NAr)₂Mo(η-C₇H₇)] (2), which is the first example of a transition-metal imido compound with a η-cycloheptatrienyl ligand.     

Fullerene C60 as a η5- and η6-ligand in sandwich-type π-complexes with transition metals

The molecular and electronic structures of some hypothetical sandwich-type -complexes of transition metals with fullerene C₆₀ were modeled. The M-C₆₀ bonds in ⁵-C₆₀MCp⁺ complexes (M = Fe, Ru, Os) are less strong than the M-Cp bonds in ferrocene, ruthenocene, and osmocene, respectively. The ⁶-C₆₀MC₆H₆ complexes (M = Cr, Mo, W) should be less stable than their classical analogs (C₆H₆)M(C₆H₆). The coordination of a metal atom with the fullerene at its pentagonal face is more energetically favorable than at a hexagonal face.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 598–601, April, 1994.We are grateful to V. I. Sokolov for discussion of the results obtained. This study was supported by the Russian Foundation for Basic Research (grants 93-03-4101 and 93-03-18725).     

Reactions of chelated η-pentadienyl iron complexes with nucleophiles

Ferracyclic (1-3-η³)pentadienyl complexes with electronically decoupled allyl and vinyl moieties were reacted with various heteroatom and carbon nucleophiles. Primary amines selectively attacked neutral (4-6-η³-pentadienyl)ferralactones 2 on the end of the allyl ligand to give 3-(endo-vinyl)-(4-6-η³-allyl)ferralactams 4 and by a similar reaction of the latter eventually 6-(exo-vinyl)-(4-6-η³-allyl)ferralactams 5. -like attack on the conjugated coplanar vinyl residue of 2 was not observed. The cationic η³-allyl complex 3 was attacked by nucleophiles either on the allylic terminus furnishing free (1Z, 3E)-dienes 8, or on the vinyl residue which is part of an activated Michael system to give η⁴-1,3-diene complexes 9. η⁴-1,3,5-Triene complex 10 was obtained with basic nucleophiles.     

Chiral discrimination at the η3-allyl units of rhodium(I) η3-cyclo-octenyl complexes containing chiral bidentate phosphanes

A three step synthesis of rhodium(I) η³-cyclooctenyl complexes [(P₂*)Rh(η³-C₈H₁₃)] (P₂*=chiral bidentate phosphane) starting from commercially available [{(cod)Rh(μ-Cl)}₂] is described. Examination of these complexes by multinuclear NMR-spectroscopy reveals a distinct stereochemical differentiation of the terminal positions of the η³-allyl unit. Preliminary results on the reactivity of these compounds towards various electrophiles are reported.     

Hydrogen-bonded networks from η-semiquinone complexes of manganese tricarbonyl

The cationic manganese tricarbonyl complexes containing η⁶-2-methylhydroquinone (2a), η⁶-2,3-dimethylhydroquinone (3a), η⁶-2-t-butylhydroquinone (4a), η⁶-tetramethylhydroquinone (5a) and η⁶-4,4′-biphenol (6a) are readily deprotonated to the corresponding neutral (η⁵-semiquinone)Mn(CO)₃ (2b-6b) and anionic (η⁴-quinone)Mn(CO)₃⁻ (2c-5c) complexes. The X-ray structures of 2b-6b feature strong intermolecular hydrogen bonding interactions that result in the formation of supramolecular organometallic networks. Significantly, the substitution pattern at the semiquinone ring affects the stereochemistry of the hydrogen bonding interactions. NMR spectra of 2b, 3b and 5b reveal dynamic hydrogen bonding in solution.     

Exohedral η5-π-complexes of fullerene C20

The problem of stabilization of polyhedral carbon clusters, which do not obey the isolated pentagon rule, is discussed taking a dodecahedral fullerene C₂₀ as an example. Ab initio MO LCAO calculations in the HF/3-21G approximation showed that fullerene C₂₀ as well as its C₂₀H₅ hydrides with C _5v symmetry can form stable 2⁵--complexes of the CpFeC₂₀FeCp and H₅C₂₀FeC₂₀H₅ types. The energies of the ⁵-Fe--C₂₀ -bonds in these complexes were compared with those of the Fe--Cp bond in ferrocene and the Fe--C₆₀ bond in the ⁵--C₆₀H₅FeCp complex.     

Flash-vacuum pyrolysis of η5-cyclopentadienyl-dicarbonylcobalt. formation of cobaltocene

Flash-vacuum pyrolysis (350°C, 0.1 Torr) of cyclopentadienyldicarbonylcobalt [CpCo(CO)₂] afforded cobaltocene (85% yield) at the end of the pyrolysis tube. This compound is formed in a bimolecular reaction in the hot zone of the tube between species from which CO ligands have been lost.     

Acetylation and benzoylation of η5,η5-fulvalenedimanganesehexacarbonyl

⁵,⁵-Fulvalenedimanganesehexacarbonyl (dicymantrenyl) was acetylated and benzoylated by RC(O)Cl+AlCl₃ in CH₂Cl₂, under conditions of the Friedel-Crafts reaction. The reaction involves both nonequivalent positions of the cyclopentadienyl rings to give mixtures of two isomeric ketones. When using an excess of the acetylating mixture, diacetyl derivatives of dicymantrenyl were obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2017–2020, October, 1995.The authors are grateful to P. V. Petrovsky and E. V. Vorontsov (the NMR laboratory of the Institute of Organoelement Compounds, Russian Academy of Sciences) for recording¹H NMR spectra.     

Hydroxylation of azomethine carbon: isolation of complexes of η5 and η6-cyclic hydrocarbon platinum group metals with a new Schiff-base ligand

A new Schiff base, (pyridin-2-yl)-N-(3,5-di(pyridin-2-yl)-4H-1,2,4-triazol-4-yl)methanimine, (L), was synthesized. Reaction of [(η⁶-arene)Ru(µ-Cl)Cl]₂ and [Cp*M(µ-Cl)Cl]₂ (M = Rh and Ir) with one equivalent of L in the presence of NH₄PF₆ in methanol yielded dinuclear complexes, [(η⁶-arene)₂Ru₂(L-OH)Cl](PF₆)₂ {arene = C₆H₆ (1), p-ⁱPrC₆H₄Me (p-cymene) (2) and C₆Me₆ (3)}, and [Cp*₂M₂(L-OH)Cl](PF₆)₂ [M = Rh (4) and Ir (5)], respectively, leading to the formation of five new chiral complexes with –OH on the azomethine carbon. L is a pentadentate ligand where one of the metal centers is coordinated to two nitrogen atoms in a bidentate chelating fashion while the other metal is bonded tridentate to three nitrogen atoms. Although the ligand is neutral before coordination, after complexation it is anionic (uni-negative) with negative charge on the azo nitrogen {see the structures: N(5) in 2[PF₆]₂ and N(3) for 4[PF₆]₂}. The complexes have been characterized by various spectroscopic methods including infrared and ¹H NMR and the molecular structures of the representative complexes are established by single-crystal X-ray diffraction studies.     

A Highly Asymmetric Gold(III) η3-Allyl Complex

A highly asymmetric Au^III η³-allyl complex has been generated by treating Au(η¹-allyl)Br(tpy) (tpy=2-(p-tolyl)pyridine) with AgNTf₂. The resulting η³-allyl complex has been characterized by NMR spectroscopy and X-ray crystallography. DFT calculations and variable temperature ¹H NMR suggest that the allyl ligand is highly fluxional.     

Study of novel η-cyclopentadienyl and η-arene platinum group metal complexes containing a N4-type ligand and their structural characterization

The mononuclear η⁵-cyclopentadienyl complexes [(η⁵-C₅H₅)Ru(PPh₃)₂Cl], [(η⁵-C₅H₅)Os(PPh₃)₂Br] and pentamethylcyclopentadienyl complex [(η⁵-C₅Me₅)Ru(PPh₃)₂Cl] react in the presence of 1 eq. of the tetradentate N,N′-chelating ligand 3,5-bis(2-pyridyl)pyrazole (bpp-H) and 1 eq. of NH₄PF₆ in methanol to afford the mononuclear complexes [(η⁵-C₅H₅)Ru(PPh₃)(bpp-H)]PF₆ ([1]PF₆), [(η⁵-C₅H₅)Os(PPh₃)(bpp-H)]PF₆ ([2]PF₆) and [(η⁵-C₅Me₅)Ru(PPh₃)(bpp-H)]PF₆ ([3]PF₆), respectively. The dinuclear η⁵-pentamethylcyclopentadienyl complexes [(η⁵-C₅Me₅)Rh(μ-Cl)Cl]₂ and [(η⁵-C₅Me₅)Ir(μ-Cl)Cl]₂ as well as the dinuclear η⁶-arene ruthenium complexes [(η⁶-C₆H₆)Ru(μ-Cl)Cl]₂ and [(η⁶-p-ⁱPrC₆H₄Me)Ru(μ-Cl)Cl]₂ react with 2 eq. of bpp-H in the presence of NH₄PF₆ or NH₄BF₄ to afford the corresponding mononuclear complexes [(η⁵-C₅Me₅)Rh(bpp-H)Cl]PF₆ ([4]PF₆), [(η⁵-C₅Me₅)Ir(bpp-H)Cl]PF₆ ([5]PF₆), [(η⁶-C₆H₆)Ru(bpp-H)Cl]BF₄ ([6]BF₄) and [(η⁶-p-ⁱPrC₆H₄Me)Ru(bpp-H)Cl]BF₄ ([7]BF₄). However, in the presence of 1 eq. of bpp-H and NH₄BF₄ the reaction with the same η⁶-arene ruthenium complexes affords the dinuclear salts [(η⁶-C₆H₆)₂Ru₂(bpp)Cl₂]BF₄ ([8]BF₄) and [(η⁶-p-ⁱPrC₆H₄Me)₂Ru₂(bpp)Cl₂]BF₄ ([9]BF₄), respectively. These compounds have been characterized by IR, NMR and mass spectrometry, as well as by elemental analysis. The molecular structures of [1]PF₆, [5]PF₆ and [8]BF₄ have been established by single crystal X-ray diffraction studies and some representative complexes have been studied by UV–vis spectroscopy.     

1,3-Dipolar cycloaddition reaction of nitrone η6-(arene)chromium tricarbonyl complexes with styrene and η6-(styrene)chromium tricarbonyl

The products of 1,3-dipolar cycloaddition of the nitrone-type η⁶-(arene)chromium tricarbonyl complexes (CO)₃CrC₆H₅CH=N⁺(O^?)R, where R = Me, Ph, Bu^t, with styrene and η⁶-(styrene)chromium tricarbonyl were obtained and characterized by a combination of physicochemical methods. This type of reactions proceeded with very high regio- and stereoselectivity to exclusively form cis-2,3,5-tri-substituted isoxazolidines.