Iron and ruthenium triple-decker complexes with a central pentaphospholyl ligand

Thirty-electron triple-decker complexes with a central pentaphospholyl ligand [(η-C₅Me₅)Fe(μ-η:η-P₅)M(η-C₅R₅)]BF₄ (M=Fe, R=Me or M=Ru, R=H, Me) were synthesized by a stacking reaction of cationic 12-electron fragments [(η-C₅R₅)M]⁺ with (η-C₅Me₅)Fe(η-P₅). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1625–1626, August, 1998.     

Synthesis of dicationic triple-decker complexes with a central B-cyclohexyl-substituted borole ligand

Stacking reactions of the dicationic fragments [LM]²⁺ (LM = (-C₆H₆)Ru, (-C₆H₃Me₃)Ru, or (-C₅Me₅)Rh) with the complex (-C₅H₅)Co(-C₄H₄BCy) (Cy = cyclo-C₆H₁₁) afforded new dicationic 30-electron triple-decker complexes [(-C₅H₅)Co(-:-C₄H₄BCy)ML](BF₄)₂ containing a cyclohexyl-substituted borole ligand in the central position.     

Synthesis of triple-decker iron and cobalt complexes with a central tetramethylphospholyl ligand

30-Electron triple-decker complexes [(η-C₅H₅)Fe(μ-η:η-C₄Me₄P)Fe(η-C₅Me₅)]PF₆ and [(η-C₄Me₄)Co(μ-η:η-C₄Me₄P)Fe(η-C₅Me₅)]PF₆ with a central tetramethylphospholyl ligand were synthesized by stacking reactions of cationic fragments [(η-C₅H₅)Fe]⁺ and [(η-C₄Me₄)Co]⁺ with nonamethylphosphaferrocene (η-C₄Me₄P)Fe(η-C₅Me₅). Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1647–1649, September, 2000.     

The first metallacarborane triple-decker complexes with a bridging borole ligand

The (borole)iodide complex [(η⁵-C₄H₄BPh)RhI]₄ reacts with the carborane anion [Carb′]⁻ (Carb′ = 9-SMe₂-7,8-C₂B₉H₁₀) giving (Carb′)Rh(η⁵-C₄H₄BPh) (2). Reactions of 2 with dicationic fragments [LM]²⁺ afford the μ-borole triple-decker complexes [(Carb′)Rh(μ-η⁵:η⁵-C₄H₄BPh)ML]²⁺ [LM = Cp^∗Ir (4), (Carb′)Rh (7)] or the arene-type complexes [(Carb′)Rh(μ-η⁵:η⁶-C₄H₄BPh)ML]²⁺ [LM = Cp^∗Rh (3), (Carb′)Ir (8)]. The structure of 4(BF₄)₂ was determined by X-ray diffraction.     

Synthesis of the first unsymmetrical 34-electron cationic cobalt-nickel triple-decker complex with a central cyclopentadienyl ligand [(η-C6Me6)Co(μ-η:η-C5H5)Ni(η-C5H5)]PF6

The first unsymmetrical 34-electron cationic cobalt-nickel triple-decker complex with a central cyclopentadienyl ligand [(η-C₆Me₆)Co(μ-η:η-C₅H₅)Ni(η-C₅)PF₆ was prepared by the reaction of [(η-C₆Me₆)₂Co]PF₆ with nickelocene. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 798–799, April, 1999.     

Structures of cationic metallacarborane complexes [(η-9-Me2S-7,8-C2B9H10)Ni(μ-Cp)Ni(η-9-Me2S-7,8-C2B9H10)]+ and [Cp*Ru(Me2S-C2B9H10)RuCp*]+

The structures of the metallacarborane cations [(-9-Me₂S-7,8-C₂B₉H₁₀)Ni(-Cp)Ni(-9-Me₂S-7,8-C₂B₉H₁₀)]⁺ (2) and [Cp*Ru(Me₂S-C₂B₉H₁₀)RuCp*]⁺ (4b) were established by X-ray diffraction analysis. These results confirmed the triple-decker structure proposed for complex 2 earlier, whereas complex 4b proved to be 13-vertex dimetallacarborane rather than the triple-decker complex, as has been suggested earlier.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1879–1883, September, 2004.     

Synthesis of metallacarborane triple-decker complexes with the bridging diborolyl ligand

Triple-decker complexes CpCo(μ-1,3-C₃B₂Me₅)M(η-7,8-C₂B₉H₁₁) (M = Rh (3), Ir (4)) were synthesized by the reaction of [CpCo(μ-1,3-C₃B₂Me₅)MBr₂]₂ (M = Rh, Ir) with Tl[TlC₂B₉H₁₁]. The structure of 3 was established by X-ray diffraction analysis.     

Rhodium-containing triple-decker complexes with a central borole ligand

Triple-decker complexes with a bridging borole ligand (C₄H₄BPh)Rh(μ-C₄H₄BPh)ML (ML = RuCp, 2a; RuCp^∗, 2b; FeCp^∗, 3; Co(C₄Me₄), 4; Ir(cod), 5) were synthesized by stacking reactions of [Rh(C₄H₄BPh)₂]⁻ (1) with cationic [ML]⁺ fragments. The structures of 2a,b and (C₄H₄BPh)Rh(μ-C₄H₄BPh)Rh(C₄H₄BPh) (6) were determined by X-ray diffraction.     

New triple-decker complexes prepared by the stacking reactions of cationic metallofragments with sandwich compounds

The results of our recent studies devoted to the synthesis of cationic triple-decker complexes are summarized. The stacking reactions of cationic metallofragments with sand-with compounds can be used as a general method for the synthesis of these complexes. This method was used for the preparation of 30- and 34-electron cationic triple-decker complexes containing cyclopentadienyl and pentaphospholyl ligands in the bridging position and carbocycles C _n H _n (n=4–7) and carboranes as terminal ligands. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1636–1642, September, 1999.     

Dicationic triple-decker complexes with a bridging boratabenzene ligand

New dicationic triple-decker complexes with a bridging boratabenzene ligand [Cp*Fe(μ-η:η-C₅H₅BMe)ML]X₂ (ML=CoCp*, 6(CF₃SO₃)₂; RhCp, 7(BF₄)₂; IrCp, 8(CF₃SO₃)₂; Ru(η-C₆H₆), 9(CF₃SO₃)₂; Ru(η-C₆H₃Me₃-1,3,5), 10(CF₃SO₃)₂; Ru(η-C₆Me₆), 11(CF₃SO₃)₂) were synthesized by stacking reactions of Cp*Fe(η-C₅H₅BMe) (2) with the corresponding half-sandwich fragments [ML]²⁺. The structure of 10(CF₃SO₃)₂ was determined by X-ray diffraction study.     

Triple-decker complexes with a central borole ligand C<Subscript>4</Subscript>H<Subscript>4</Subscript>BR

The review summarizes the results of the recent author’s research on the synthesis of triple-decker complexes with bridging borole ligand. Electrophilic stacking of sandwich compounds with [(ring)M] ⁿ⁺ (n = 1, (ring)M = (C₅R₅)Ru, (C₄Me₄)Co; n = 2, (ring)M = Cp*Co, Cp*Rh, etc.) cationic fragments were used as a general method of synthesis of the complexes. The influence of the substituent at the boron atom on the course of stacking reactions is discussed. The spectral, structural, and electrochemical properties of the complexes synthesized are also considered. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 1–7, January, 2008.     

Ruthenium naphthalene complexes with a carboxy-substituted cyclopentadienyl ligand

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Synthesis of cationic indenyl- and fluorenyl-arene complexes of ruthenium

Interaction of [Ru(-C ₆ H ₆ )Cl ₂ ] ₂ with indenyl- or fluorenyllithium in THF gives, together with cationic benzene complexes [Ru( ⁵ -C ₉ H ₇ )(-C ₆ H ₆ )]⁺ and [Ru( ⁵ -C ₁₃ H ₉ )(-C ₆ H ₆ )]⁺, the neutral cyclohexadienyl derivatives Ru( ⁵ -C ₉ H ₆ -C ₉ H ₇ ) and Ru( ⁵ -C ₁₃ H ₉ )( ⁵ -C ₆ H ₆ -C ₁₃ H ₉ ), respectively. Interaction of the cyclohexadienyl complexes with Al ₂ O ₃ , Ph ₃ C⁺, and CF ₃ CO ₂ H has been studied. Reaction of Ru( ⁵ -C ₁₃ H ₉ )( ⁵ -C ₆ H ₇ ) with CF ₃ CO ₂ H in the presence of an arene yields cationic cyclohexadienylarene complexes: [Ru( ⁵ -C ₁₃ H ₉ )( ⁶ -arene)]⁺ (arene=C ₆ H ₆ or 1,3,5-Me ₃ C ₆ H ₃ ).A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 699–706, March, 1992.     

环戊二烯基轻稀土二氯化物邻菲罗啉配合物的合成

用LnCl~3邻菲绕啉和C~5H~5Na在四氢呋喃中的反应合成了四个1,10-二氮杂菲配位的含四氢呋喃的轻稀土环戊二烯二氯化物。用元素分析、红外光谱、电子能谱、差热分析等方法鉴定了这四个新化合物。     

Synthesis and properties of Zr-Co heterodinuclear complexes with a bridging bis(cyclopentadienyl) ligand

[(η⁵-C₅H₅)ZrCl₂(η⁵-C₅H₄)CMe₂(C₅H₅)] reacted with Co₂(CO)₈ to produce a heterodinuclear Zr(IV)-Co(I) complex [(η⁵-C₅H₅)ZrCl₂(η⁵-C₅H₄)CMe₂(η⁵-C₅H₄)Co(CO)₂] (3). Complex 3 underwent oxidative addition of I₂ to give [(η⁵-C₅H₅)ZrCl₂(η⁵-C₅H₄)CMe₂(η⁵-C₅H₄)CoI₂(CO)] (4) having Zr(IV) and Co(III) centers. The carbonyl ligand of 4 was easily replaced with P(OMe)₃ and PPh₃ to afford [(η⁵-C₅H₅)ZrCl₂(η⁵-C₅H₄)CMe₂(η⁵-C₅H₄)CoI₂(L)] (5: L = P(OMe)₃, 6: L = PPh₃). Structures of 5 and 6 were determined by X-ray crystallography. These Zr-Co heterodinuclear complexes catalyzed polymerization of ethylene and propylene.     

Synthesis and structure of half-sandwich SmII and YIII cyclopentadienyl halide complexes with the penta(benzyl)cyclopentadienyl ligand

Russian Chemical Bulletin - The exchange reactions of equimolar amounts of potassium penta(benzyl)cyclopentadienide CpBn5K (CpBn5 = C5(CH2Ph)5) and SmI2(THF)2 or YCl3 afforded the corresponding...