Palladium(II) compounds with planar chirality. X-Ray crystal structures of (+)-(R)-[{(η5-C5H4)–CHN–CH(Me)–C10H7}Fe(η5-C5H5)] and (+)-(Rp,R)-[Pd{[(Et–CC–Et)2(η5-C5H3)–CHN–CH(Me)–C10H7]Fe(η5-C5H5)}Cl]

A wide variety of planar chiral cyclopalladated compounds of general formulae [Pd{[(η⁵-C₅H₃)–CHN–CH(Me)–C₁₀H₇]Fe(η⁵-C₅H₅)}Cl(L)] (with L=py-d₅ or PPh₃), [Pd{[(η⁵-C₅H₃)–CHN–CH(Me)–C₁₀H₇]Fe(η⁵-C₅H₅)}(acac)] or [Pd{[(R¹–CC–R²)₂(η⁵-C₅H₃)–CHN–CH(Me)–C₁₀H₇]Fe(η⁵-C₅H₅)}Cl] (with R¹=R²=Et; R¹=Me, R²=Ph; R¹=H, R²=Ph; R¹=R²=Ph; R¹=R²=CO₂Me or R¹=CO₂Et, R²=Ph) are reported. The diastereomers {(R_p,R) and (S_p,R)} of these compounds have been isolated by either column chromatography or fractional crystallization. The free ligand (R)-(+)-[{(η⁵-C₅H₄)–CHN–CH(Me)–C₁₀H₇}Fe(η⁵–C₅H₅)] (1) and compound (+)-(R_p,R)-[Pd{[(Et–CC–Et)₂(η⁵-C₅H₃)–CHN–CH(Me)–C₁₀H₇]Fe(η⁵-C₅H₅)}Cl] (7a) have also been characterized by X-ray diffraction. Electrochemical studies based on cyclic voltammetries of all the compounds are also reported.     

Synthetic applications of the photolysis of the cyclopentadienyliron-(ρ-xylene) cation

Photolysis of CpFe(ρ-xylene)⁺ (Cp = η⁵-cyclopentadienyl) in the presence of suitable 6- or 2-electron donor ligands results in replacement of the aromatic ring with one 6-electron or three 2-electron donor ligands. The compounds [CPFe(η⁶-C₇H₈)]BF₄ (C₇H₈ = cycloheptatriene), [CpFe(η⁶-C₈H₈)]PF₆, (C₈H₈ = cyclooctatetraene), [CpFe(η⁶-PCP)]PF₆ (PCP = 2,2-paracyclophane), [CpFe-(P(OCH₃)₃)₃]PF₆ and [CpFe(P(OCH₂CH₃)₃)₃]PF₆ were prepared in this manner. The compound [CpFe(TM4)₃FeCp](PF₆)₂ · CH₃COCH₃ (TM4 = 2,5-dimethyl-2,5 diisocyanohexane) was prepared in two steps. First, [CpFe(ρ-xylene)]PF₆ was irradiated with an excess of the free TM4 ligand producing a mixture of [CpFe(TM4)₃]⁺ and [CpFe(TM4)₃FeCp]²⁺. An additional equivalent of [CpFe(p-xylene)]PF₆ was added to this mixture and photolysis yielded [CpFe(TM4)₃FeCp](PF₆)₂ · CH₃COCH₃.     

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.     

New η-allyl η-cyclopentadienylcobalt cations

[Co(R-η-C₃H₄)(η-C₅H₅)I] is a good precursor for the preparation of some new cationic complexes as the iodide can easily be replaced; thus addition of PEt₃ to the iodo-complex (R  H) gives [Co(η-C₃H₅)(η-C₅H₅)(PEt₃)]⁺. The reactions of [Co(R-η-C₃H₄)(η-C₅H₅))I] (R  H or 2-Me) with AgBF₄ give solutions containing the coordinatively unsaturated species [Co(R-η-C₃H₄)(η-C₅H₅)⁺. The presence of traces of water leads to the formation of [Co(R-ηC₃H₄)-(η-C₅H₅)(H₂O)]⁺. The addition of monodentate ligands L  PEt₃ PPh₃, AsPh₃, SbPh₃, CNCH₃ and bidentate ligands LL  Ph₂PCH₂CH₂PPh₂(dppe) and o-C₆H₄(AsMe₂)₂(diars), gives, respectively mononuclear [Co(2-Me-ηC₃H₄)-(η-C₅H₅)L]⁺ and binuclear ligand-bridged [(2-Me-ηC₃H₄)(η-C₅H₅)CoLLCo(2-Me-ηC₃H₄)(η-C₅H₅))]²⁺ complexes. Crystals of [Co(2-Me-ηC₃H₄)(η-C₅H₅)-(H₂O)]⁺[BF₄]^- are monoclinic, space group P2₁/c, with a 7.858(3), b 10.262(4), c 15.078(4) Å, β 98.36(1)°. The molecular structure contains the cobalt atom bonded to planar 2-Me-allyl and cyclopentadienyl substituents, which are almost parallel with the H₂O molecule in a staggered conformation with respect to the 2-Me group.     

Organodiiron(II)-complexes containing a long conjugated hydrazonato spacer. Synthesis, characterization, electrochemical and structural studies

Organometallic hydrazines of general formula [(η⁵-Cp)Fe(η⁶-p-RC₆H₄NHNH₂)]⁺PF₆⁻ (Cp=C₅H₅; R=H, (1)⁺PF₆⁻; Me, (2)⁺PF₆⁻; MeO, (3)⁺PF₆⁻; Cl, (4)⁺PF₆⁻) react with equimolar quantities of (E)-4-(2-ferrocenylvinyl)-benzaldehyde, (E)-[(η⁵-Cp)Fe(η⁵-C₅H₄)CHCHC₆H₄CHO], to afford stereoselectively, the new homodimetallic hydrazones formulated as (E)-[(η⁵-Cp)Fe(η⁶-p-RC₆H₄)NHNCHC₆H₄CHCH(η⁵-C₅H₄)Fe(η⁵-Cp)]⁺PF₆⁻ (R=H, (5)⁺PF₆⁻; Me, (6)⁺PF₆⁻; MeO, (7)⁺PF₆⁻; Cl, (8)⁺PF₆⁻). These compounds were fully characterized by elemental analysis and spectroscopic techniques (¹H- and ¹³C-NMR, IR and UV-vis) and, in the case of complex (6)⁺PF₆⁻, by single crystal X-ray diffraction methods. The rotations of the ferrocenyl unit by 37.2° out of the NHNCHC₆H₄CHCH spacer and coordinated phenyl ring planes, may generate an unfavorable structure to allow π-electron delocalization along the entire hydrazonato backbone between the two metals separated through bonds by more than 1.8 nm, as confirmed by the electrochemical data.     

Study of half-sandwich platinum group metal complexes bearing dpt-NH2 ligand

A quite general approach for the preparation of η⁵-and η⁶-cyclichydrocarbon platinum group metal complexes is reported. The dinuclear arene ruthenium complexes [(η⁶-arene)Ru(μ-Cl)Cl]₂ (arene = C₆H₆, C₁₀H₁₄ and C₆Me₆) and η⁵-pentamethylcyclopentadienyl rhodium and iridium complexes [(η⁶-C₅Me₅)M(μ-Cl)Cl]₂ (M = Rh, Ir) react with 2 equiv. of 4-amino-3,5-di-pyridyltriazole (dpt-NH₂) in presence of NH₄PF₆ to afford the corresponding mononuclear complexes of the type [(η⁶-arene)Ru(dpt-NH₂)Cl]PF₆ {arene = C₁₀H₁₄ (1), C₆H₆ (2) and C₆Me₆ (3)} and [(η⁶-C₅Me₅)M(dpt-NH₂)Cl]PF₆ {M = Rh (4), Ir (5)}. However, the mononuclear η⁵-cyclopentadienyl analogues such as [(η⁵-C₅H₅)Ru(PPh₃)₂Cl], [(η⁵-C₅H₅)Os(PPh₃)₂Br], [(η⁵-C₅Me₅)Ru(PPh₃)₂Cl] and [(η⁵-C₉H₇)Ru(PPh₃)₂Cl] complexes react in presence of 1 equiv. of dpt-NH₂ and 1 equiv. of NH₄PF₆ in methanol yielded mononuclear complexes [(η⁵-C₅H₅)Ru(PPh₃)(dpt-NH₂)]PF₆ (6), [(η⁵-C₅H₅)Os(PPh₃)(dpt-NH₂)]PF₆ (7), [(η⁵-C₅Me₅)Ru(PPh₃)(dpt-NH₂)]PF₆ (8) and [(η⁵-C₉H₇)Ru(PPh₃)(dpt-NH₂)]PF₆ (9), respectively. These compounds have been totally characterized by IR, NMR and mass spectrometry. The molecular structures of 4 and 6 have been established by single crystal X-ray diffraction and some of the representative complexes have also been studied by UV–Vis spectroscopy.     

Syntheses,spectroscopic and structural studies of indenyl ruthenium complexes incorporating amine and nitrile ligands: molecular structures of [(η5-C9H7) Ru(η2-dppe)(CH3CN)]PF6 and [(η5-C9H7)Ru(η2-dppe)(NH3)]PF6

The reaction of [(η⁵-C₉H₇)Ru(η²-dppe)Cl] (1) with monodentate nitriles, (L) in the presence of NH₄PF₆ afforded the complexes [(η⁵-C₉H₇)Ru(η²-dppe)(L)]PF₆, with L?=?CH₃CN (2a), CH₃CH=CHCN (2b), NCC₆H₄CN (2c), C₆H₅CH₂CN (2d), respectively. However, reaction of 1 with NH₄PF₆ in methanol yielded an amine complex of the type [(η⁵-C₉H₇) Ru(η²-dppe)(NH₃)]PF₆ (3a). The complexes were fully characterized by spectroscopy and analytical data. The molecular structures of the complexes [(η⁵-C₉H₇)Ru(η²-dppe) (CH₃CN)]PF₆ (2a) and [(η⁵-C₉H₇)Ru(η²-dppe)(NH₃)]PF₆ (3a) have been determined by single crystal X-ray analyses.     

Darstellung und Charakterisierung von kationischen η2-1-Buten- und Acetonitrilkomplexen

Preparation and Characterization of Cationic η²-1-Butene and Acetonitrile Complexes The reaction of the species η⁵-C₅H₅M(CO)_n-σ-C₄H₇ (M = Fe, Mo, W; n = 2, 3) with (C₆H₅)₃CBF₄ yielded – instead of the expected cationic butadiene complexes of the type [η⁵-CpM(CO)_n?1-η⁴-C₄H₆][BF₄], which would have been formed in case of hydride cleavage – compounds of the type [η⁵-CpM(CO)_n η²-C₄H₈][BF₄], which were formed by protonation of the σ-C₄H₇ ligands. The reaction proceeded quantitatively. The BF₄^? anion can be substituted by other anions, such as ClO₄^?, B(C₆H₅)₄^?, PF₄^?, and [Cr(SCN)₄(NH₃)₂]^? in the complexes obtained. The mechanism of the reaction leading to the η²-bonded 1-butene complexes was determined by isotope experiments. In trying to recrystallize the butene complexes from acetonitrile the cationic complexes [η⁵-C₅H₅ Fe(CO)₂CH₃CN]BF₄ and [η⁵-C₅H₅ M(CO)₃CH₃CN]BF₄ were observed; the X-ray structure analysis of the former is reported.     

Effektive synthese und kristallstruktur von [CpFe(η6-C8H8)]PF6

[CpFe(η⁶-C₈H₈)]PF₆ (C₈H₈ = cyclooctatetraene) is obtained in high yields by the photolysis of [CpFe(η⁶-C₆H₆)]PF₆ in the presence of an excess of C₈H₈. An X-ray diffraction study of [CpFe(η⁶-C₈H₈)]PF₆ has confirmed the η⁶-bonding mode of the C₈H₈ ligand, which had been shown to exist by NMR spectroscopy. The uncomplexed C,C double bond is strongly bent away from the plane of the coordinated C₆-unit of the C₈H₈ ligand.     

[(η-C6H6)Ru(L)(Cl/N3/CN/CH3CN)] complexes of non-planar pyrazolylmethylpyridine ligands: Formation of helices due to C-H?X (X = Cl, N) interaction

Structural analysis of a previously reported half-sandwich complex having three-legged “piano-stool” geometry [(η⁶-C₆H₆)Ru^II(L¹)Cl][PF₆] (1) (L¹ = 2-(pyrazol-1-ylmethyl)pyridine) is described. Treatment of 1 with (i) Ag(CF₃SO₃) in CH₃CN and (ii) NaN₃ in CH₃OH, and (iii) the reaction between [(η⁶-C₆H₆)Ru(L²)Cl]-[PF₆] (2) (previously reported) and NaCN in C₂H₅OH led to the isolation of [(η⁶-C₆H₆)Ru(L¹)(CH₃CN)][PF₆]₂ (3), [(η⁶-C₆H₆)Ru(L¹)(N₃)][PF₆] (4), and [(η⁶-C₆H₆)Ru(L²)(CN)][PF₆] (5), respectively (L² = 2-(3,5-dimethyl-pyrazol-1-ylmethyl)pyridine). The complex [(η⁶-C₆H₆)Ru(L⁴)Cl][PF₆] (6) with a new ligand (L⁴ = 2-[3-(4-fluorophenyl)pyrazol-1-ylmethyl]pyridine) has also been synthesized. The structures of 3-6 have been elucidated (¹H NMR spectra; CD₃CN). The molecular structures of 1, 4, and 6·C₆H₅CH₃ have been determined. Notably, the crystal-packing in these structures is governed by C-H?X (X = Cl, N) interactions, generating helical architectures.     

The [Cp(CO)2Fe] (Fp) group as a donor in donor/acceptor substituted disilanes: synthesis,structure and electronic properties of FpSi2Me4C6H4CHC(CN)2

UV–vis absorption spectroscopy and cyclic voltammetry are used to study electronic interactions in the donor/acceptor substituted disilane FpSi₂Me₄C₆H₄CHC(CN)₂ (Fp=η⁵-C₅H₅Fe(CO)₂) (1). The synthesis of 1 was achieved by a conventional chemical route, the model substances FpSiMe₃ (2), FpSi₂Me₅ (3) and FpSi₂Me₄C₆H₅ (4) were obtained by the electrolysis of Fp₂ in the presence of the appropriate chlorosilane. The structure of 1, determined by X-ray diffraction, exhibits an all-trans-array of the FeSiSiC_aryl fragment, a basic requirement for optimal through-bond interaction. UV–vis and CV data indicate strong intramolecular donor/acceptor interaction in 1.     

π-cyclopentadienyls of nickel(II) : XV. Insertion reaction of RNCS into the nickel—carbon bond

η⁵-C₅H₅NiPBu₃CH(CN)₂ (I) readily undergoes ethyl- or phenyl-isothiocyanate insertion, producing the stable products η⁵-C₅H₅NiPBu₃SC(NRH) = C(CN)₂ (IIIa; R = C₂H₅, IIIb; R = C₆H₅. η⁵-C₅H₅NiPPh₃CH(CN)₂ (II) reacts with RNCS (R = C₂H₅ and C₆H₅) to undergo two types of insertion reaction; with C₂H₅NCS, η⁵C₅H₅NiPPh₃SC[N(C₂H₅)H] = C(CN)₂ (IVa) is obtained, with C₆H₅NCS, on the other hand, η⁵-C₅H₅NiPPh₃SC(NC₆H₅)CH(CN)₂ (IVb) is produced. p ]IIIa and IIIb react with PBu₃ to give ionic complexes [η⁵-C₅H₅Ni(PBu₃)₂]⁺ [SC(NC₂H₅H)C(CN)₂]^? (Va) and [η⁵-C₅H₅Ni(PBu₃)₂]⁺ [SC(NC₆H₅)CH(CN)₂]^?(Vb), respectively.     

Facile synthesis of new polyolefinic ruthenium(0) complexes from ruthenium(II) precursors

The new ruthenium(II) complex [(C₈H₁₀)RuCl₂]_n (1) (C₈H₁₀ = 1,3,5-cyclooctatriene; n ⩾ 2) has been obtained from the reaction of RuCl₃·xH₂O with 1,3,5,7-cyclooctatetraene in refluxing ethanol. Reduction of [(C₈H₁₀)RuCl₂]_n and [(C₇H₈)RuCl₂]₂ (2) (C₇H₈ = 1,3,5-cyclooctatriene) by Na/Hg amalgam in the presence of isoprene (C₅H₈) gives the novel ruthenium(O) complexes [(η⁶-C₈H₁₀)Ru(η⁴-C₅H₈)] (3) and [(η⁶-C₇H₈)Ru(η⁴-C₅H₈)] (4). [(η⁶-C₇H₈Ru(η⁴-C₅H₈)] reacts with CO and HBF₄ to give [(η⁶-C₇H₈)Ru(η³-C₅H₉)(CO)][BF₄] (C₅H₉ = trans-1,2-dimethylallyl (5a); 1,1-dimethylallyl (5b)).     

The structure of an arenemanganese tricarbonyl cation; synthesis and X-ray analysis of dodecahydrotriphenylene(tricarbonyl)manganese(I) tetrafluoroborate

The synthesis, spectroscopic properties, and X-ray structure of dodecahydrotriphenylene(tricarbonyl)manganese(I) tetrafluoroborate, [(η⁶-C₁₈H₂₄)Mn(CO)₃][BF₄] are reported. The cation has approximate C₃ symmetry with the MnCO vectors projected across the unbridged CC bonds of the arene ligand.     

Reactions of transition metal σ-acetylide complexes: IX. Preparation and properties of some cycloheptatrienylvinylidene complexes

Addition of [C₇H₇][PF₆] to iron, ruthenium or osmium alkynyl complexes has given eight cationic cycloheptatrienylvinylidene derivatives [M{C C(C₇H₇)R}(L)₂ (η-C₅H₅)][PF₆] (M = Fe, Ru or Os; R = Me, Pr, Ph or C₆F₅; L = PPh₃, L₂ = dppm or dppe; but not all combinations). With Fe(C₂Ph)(CO)₂(η-C₅H₅), only [Fe(CO)₂(thf)(η-C₅H₅)][PF₆] was obtained. Reactions of the new complexes are characterised by loss of the C₇H₇ group. The NMR spectra and FAB mass spectra are described in detail.     

(1,3-Diformylindenyl)cyclopentadienyl ruthenium derivatives

The reaction of [CpRu(CH₃CN)₃][PF₆], [Cp*RuCl] _n , and [Cp^FRuCl]n with 1,3-diformylindene results in the predominant formation of zwitter-ionic arene-cyclopentadienyl complexes {η⁶-1,3-(CHO)₂C₉H₅}RuCp (Cp = C₅H₅), {η⁶-1,3-(CHO)₂C₉H₅}RuCp* (Cp* = C₅Me₅), and {η⁶-1,3-(CHO)₂C₉H₅}RuCp^F (Cp^F = C₅Me₄CF₃), respectively. The ruthenocenes {η⁵-1,3-(CHO)₂C₉H₅}RuCp, {η⁵-1,3-(CHO)₂C₉H₅}RuCp*, and {η⁵-1,3-(CHO)₂C₉H₅}RuCpF were synthesized by the reaction of 1,3-diformylindenyl potassium with [CpRu(CH₃CN)₃][PF₆], [Cp*RuCl] _n , and [Cp^FRuCl] _n .     

Coordination chemistry of the [Pt2(μ-S)2(PPh3)4] metalloligand with π-hydrocarbon derivatives of d ruthenium(II), osmium(II), rhodium(III) and iridium(III)

The reactivity of [Pt₂(μ-S)₂(PPh₃)₄] towards [RuCl₂(η⁶-arene)]₂ (arene=C₆H₆, C₆Me₆, p-MeC₆H₄Prⁱ=p-cymene), [OsCl₂(η⁶-p-cymene)]₂ and [MCl₂(η⁵-C₅Me₅)]₂ (M=Rh, Ir) have been probed using electrospray ionisation mass spectrometry. In all cases, dicationic products of the type [Pt₂(μ-S)₂(PPh₃)₄ML]²⁺ (L=π-hydrocarbon ligand) are observed, and a number of complexes have been prepared on the synthetic scale, isolated as their BPh₄⁻ or PF₆⁻ salts, and fully characterised. A single-crystal X-ray structure determination on the Ru p-cymene derivative confirms the presence of a pseudo-five-coordinate Ru centre. This resists addition of small donor ligands such as CO and pyridine. The reaction of [Pt₂(μ-S)₂(PPh₃)₄] with RuClCp(PPh₃)₂ (Cp=η⁵-C₅H₅) gives [Pt₂(μ-S)₂(PPh₃)₄RuCp]⁺. In addition, the reaction of [Pt₂(μ-S)₂(PPh₃)₄] with the related carbonyl complex [RuCl₂(CO)₃]₂, monitored by electrospray mass spectrometry, gives [Pt₂(μ-S)₂(PPh₃)₄Ru(CO)₃Cl]⁺.     

Synthesis of homo- and heterodinuclear metal complexes with dimethylsilylene bridged unsymmetrical bis(cyclopentadienyl) ligand

The reaction of the dilithium salt Li₂[Me₂Si(C₅H₄)(C₅Me₄)] (2) of Me₂Si(C₅H₅)(C₅HMe₄) (1) with [MCl(C₈H₁₂)]₂ (M=Rh, Ir) and [RhCl(CO)₂]₂ afforded homodinuclear metal complexes [{Me₂Si(η⁵-C₅H₄)(η⁵-C₅Me₄)}{M(C₈H₁₂)}₂] (M=Rh: 3; M=Ir: 4) and [{Me₂Si(η⁵-C₅H₄)(η⁵-C₅Me₄)}Rh₂(CO)₂(μ-CO)] (5), respectively. The reaction of 2 with RhCl(CO)(PPh₃)₂ afforded a mononuclear metal complex [{Me₂Si(C₅HMe₄)(η⁵-C₅H₄)}Rh(CO)PPh₃] (6) leaving the C₅HMe₄ moiety intact. Taking advantage of the difference in reactivity of the two cyclopentadienyl moieties of 2, heterodinuclear complexes were prepared in one pot. Thus, the reaction of 2 with RhCl(CO)(PPh₃)₂, followed by the treatment with [MCl(C₈H₁₂)]₂ (M=Rh, Ir) afforded a homodinuclear metal complex [Rh(CO)PPh₃{(η⁵-C₅H₄)SiMe₂(η⁵-C₅Me₄)}Rh(C₈H₁₂)] (7) consisting of two rhodium centers with different ligands and a heterodinuclear metal complex [Rh(CO)(PPh₃){(η⁵-C₅H₄)SiMe₂(η⁵-C₅Me₄)}Ir(C₈H₁₂)] (8). The successive treatment of 2 with [IrCl(C₈H₁₂)]₂ and [RhCl(C₈H₁₂)]₂ provided heterodinuclear metal complex [Ir(C₈H₁₂){(η⁵-C₅H₄)SiMe₂(η⁵-C₅Me₄)}Rh(C₈H₁₂)] (9). The reaction of 2 with CoCl(PPh₃)₃ and then with PhCCPh gave a mononuclear cobaltacyclopentadiene complex [{Me₂Si(C₅Me₄H)(η⁵-C₅H₄)}Co(CPhCPhCPhCPh)(PPh₃)] (10). However, successive treatment of 2 with CoCl(PPh₃)₃, PhCCPh and [MCl(C₈H₁₂)]₂ in this order afforded heterodinuclear metal complexes [M(C₈H₁₂){(η⁵-C₅H₄)SiMe₂(η⁵-C₅Me₄)}Co(η⁴-C₄Ph₄)] (M=Rh: 11; M=Ir: 12) in which the cobalt center was connected to the C₅Me₄ moiety. Although the heating of 10 afforded a tetraphenylcyclobutadiene complex [{Me₂Si(C₅Me₄H)(η⁵-C₅H₄)}Co(η⁴-C₄Ph₄)] (13), in which the cobalt center was connected to the C₅H₄ moiety, simple heating of the reaction mixture of 2, CoCl(PPh₃)₃ and PhCCPh resulted in the formation of a tetraphenylcyclobutadiene complex [{Me₂Si(C₅H₅)(η⁵-C₅Me₄)}Co(η⁴-C₄Ph₄)] (14), in which the cobalt center was connected to the C₅Me₄ moiety. The mechanism of the cobalt transfer was suggested based on the electrophilicity of the formal trivalent cobaltacyclopentadiene moiety. In the presence of 1,5-cyclooctadiene, the reaction of 2 with CoCl(PPh₃)₃ provided a mononuclear cobalt cyclooctadiene complex [{Me₂Si(C₅Me₄H)(η⁵-C₅H₄)}Co(C₈H₁₂)] (15). The reaction of 15 with n-BuLi followed by the treatment with [MCl(C₈H₁₂)]₂ (M=Rh, Ir) afforded the heterodinuclear metal complexes of [Co(C₈H₁₂){(η⁵-C₅H₄)SiMe₂(η⁵-C₅Me₄)}M(C₈H₁₂)] (M=Rh: 16; M=Ir: 17). Treatment of 6 with Fe₂(CO)₉ at room temperature afforded a heterodinuclear metal complex [{Me₂Si(C₅HMe₄)(η⁵-C₅H₄)}{Rh(PPh₃)(μ-CO)₂Fe(CO)₃}] (18) in which the C₅HMe₄ moiety was kept intact. Treatment of dinuclear metal complex 5 with Fe₂(CO)₉ afforded a heterotrinuclear metal complex [{(η⁵-C₅H₄)SiMe₂(η⁵-C₅Me₄)}{Rh(CO)Rh(μ-CO)₂Fe(CO)₃}] (19) having a triangular metal framework. The crystal and molecular structures of 3, 11, 12, 18 and 19 have been determined by single-crystal X-ray diffraction analysis.     

Die thermische reaktion von C5H5(CO)2FeNa mit benzimidchloriden C6H5(Cl)CNR

η⁵-C₅H₅(CO)₂FeNa reacts with the benzimide chlorides C₆H₅(Cl)CNR (R  CH(CH₃)₂, C₆H₅) in boiling THF to give the η¹-iminoacyl complexes η⁵-C₅H₅ (CO)₂Fe[η¹-C(C₆H₅)NR]. Alternatively, the new Fe complexes [η⁵-C₅H₅(CO)Fe$\text{C(C}{}_6\text{H}{}_5\text{)N(CH}{}_3\text{)C(C}{}_6\text{H}{}_5\text{)N}$CH₃PF₆ (IV) and [η⁵-C₅H₅(CO)₂FeC(C₆H₅)N(CH₃)C(C₆H₅)NCH₃]PF₆ (V) are formed under the same conditions, if R  CH₃. Hudrolysis of the CN single bond of the ligand in V, not stabilized by a chelate effects as in IV, results in the formation of [η⁵-C₅H₅(CO)₂FeC(C₆H₅)NHCH₃]PF₆ (VII). Reaction of η⁵-C₅H₅(CO)₂ with N-benyzylbenzimido chloride yields η⁵-C₅H₅(CO)₂FeCH₂C₆H₅ as the only isolated product.