碳锗双桥连二环戊二烯与羰基铁的反应

碳锗双桥连二环戊二烯(Me₂C)(Me₂Ge)(C₅H₄)₂(1)与五羰基铁在回流甲苯及二甲苯中的反应,得到正常的Fe-Fe键化合物(Me₂C)(Me₂Ge)[(η⁵-C₅H₃)Fe(CO)]₂(μ-CO)₂(3)和脱锗桥产物(Me₂C)[(η⁵-C₅H₄)Fe(CO)]₂(μ-CO)₂(4)以及一个结构新颖的化合物(Me₂C)[(η⁵-C₅H₃)[(Me₂Ge)Fe(CO)₂](η¹,η⁵-C₅H₃)[Fe(CO)₂](2).用X射线衍射分析測定了化合物3的晶体结构,并提出了可能的生成机理.     

Thirty years of organometallic aryldiazenido arylazo derivatives

The aryldiazenido ligands provide the fourth member of the isoelectronic series CO, NO⁺, RNC, RN₂⁺ of ligands for transition metal complexes. The first aryldiazenido metal complex was reported in 1964 when p-CH₃OC₆H₄N₂Mo(CO)₂C₅H₅ was prepared by the reaction of NaMo(CO)₃C₅H₅ with p-CH₃OC₆H₄N₂⁺BF₄⁻. This review surveys the development of organometallic aryldiazenido chemistry since that time. Such organometallic aryldiazenido derivatives, including RN₂M(CO)₂C₅H₅, RN₂M(CO)₂(Pz₃BH) (M = Cr, Mo, W), [(η⁶-Me₆C₆)Cr(CO)₂N₂Ar]⁺, [(MeC₁₅H₄)M′(CO)₂N₂Ar]⁺ M′ = Mn, Re), [trans-PhN₂Fe(CO)₂(PPh₃)₂]⁺, and PhN₂M′(CO)₂(PPh₃)₂(PPh₃)₂ can be obtained by reactions of arenediazonium salts with suitably chosen transition metal nucleophiles. Analogous methods cannot be used to prepare alkyldiazenido transition metal complexes because of the instability of alkyldiazonium salts. However, the alkyldiazenido derivatives RCH₂N₂M(CO)₂C₅H₅ (R = H or Me₃Si) can be obtained from HM(CO)₃C₅H₅ and the corresponding diazoalkanes. Important aspects of the chemical reactivity of RN₂M(CO)₂Q derivatives (Q = C₅H₅, Pz₃BH) include CO substitution reactions, coordination of the second nitrogen in the RN₂ ligand to give heterobimetallic complexes such as C₅H₅Mo(CO)₂(μ-NNC₆H₄Me)(CO)₂C₅H₅, oxidative addition rections with X₂ X = Cl, Br, I), SnX₄, RSSR, and CINO, and reactions with further RN₂⁺ to give bis(aryldiazenido) derivatives (RN₂)₂MQL⁺ (L = CO, X⁻, etc.). Dearylation of an aryldiazenido ligand to a dinitrogen ligand can be effected by reaction of [(MeC₅H₄)M′(CO)₂N₂Ar]⁺ with certain nucleophiles to give (MeC₅H₄)M′(CO)₂N₂.     

Photochemical reactions of alkynyl iron (II) complexes with carbon disulfide. Insertion of CS2 into an iron-C(sp) bond

The novel alkynyldithiocarboxylate complexes [Fe(η⁵-C₅H₅)(S₂CCCR) (dppm-P)] (3a,b) and [Fe(η₅-C₅H₅)(S₂CCCR)(PPh₃)] (4a,b) were obtained through the insertion of CS₂ into the iron-akynyl bond in the complexes [Fe(η₅-C₅H₅)(CCR)(L)(L′] L, L′ = dppm R = Ph (1a), ^tBu(1b); L = (CO), L′ = (PPh₃) R = Ph (2a), ^tBu (2b). Variable-temperature ³¹P{¹H} NMR studies indicate the presence of two different isomers, [Fe(η⁵-C₅H₅)(η³-S,C,S′---S₂CCCR)(L)(L′)] and [Fe(η⁵-C₅H₅(η²-S,S′-S₂CCCR)(L)(L′)], which rapidly interconvert at room temperature. The synthesis of the precursor complex [Fe(η⁵-C₅H₅)(CC^tBu)(CO)(PPh₃)] is also described.     

Synthesis of tetramethyldisilane-bridged bis(1-indenyl) tetracarbonyl di-iron: A novel thermal rearrangement reaction between the Si-Si and Fe-Fe bonds

The title complex (Me₂SiSiMe₂)(η⁵-l-indenyl)Fe(CO)]₂(μ-CO)₂ (1) was prepared by the reaction of 1,2-bis(1-indenyl)tetramethyl-disilane and Fe(CO)₅ in refluxing heptane. Its thermal rearrangement product [Me₂Si(η⁵-1-indenyl)Fe(CO)₂]₂ (2) was also obtained from the reaction. 1 in refluxing xylene can be readily converted into 2. The crystal structures of the cis isomer 1c and the trans isomer 2t were determined by X-ray diffraction.     

Synthesis and reactivity towards tetrafluoroboric acid of a new family of heterobimetallic polyhydride complexes [(CO)(PPh3)2HRe(μ-H)3RhL2] (L = PPh3, 1,2,5-triphenylphosphole, or P(OMe)3)

The reaction of K[ReH₆(PPh₃)₂] with [RhCl(CO)L₂] [L= PPh₃, 1,2,5-triphenylphosphole (TPP), or P(OMe)₃] leads to the new electronically unsaturated heterobimetallic polyhydride complexes [(CO)(PPh₃)₂HRe(μ-H)₃RhL₂] in moderate-to-good yields. The structures of these complexes have been established on the basis of spectroscopic data, especially ¹H and ³¹P NMR. The bridging hydride ligands are fluxional but there is either a slow or nonexistent exchange between terminal and bridging hydrides. For L = PPh₃ or TPP, protonation with tetrafluoroboric acid affords quantitatively the cationic complexes [(CO)(PPh₃)₂HRe(μ-H)₃RhHL₂]⁺, isolated as the BF₄⁻ or the BPh₄⁻ salts.     

Synthesis and characterization of uranium(III) compounds supported by the hydrotris(3,5-dimethyl-pyrazolyl)borate ligand: Crystal structures of [U(Tp)2(X)] complexes (X = OC6H2-2,4,6-Me3, dmpz, Cl)

Reaction of [U(Tp^Me2)₂(NR₂)] (R = Ph, SiMe₃) with protic substrates such as 2,4,6-trimethylphenol (HOC₆H₂-2,4,6-Me₃), 3,5-dimethylpyrazole (Hdmpz), 2-mercaptopyridine (HSC₅H₄N) and phenylacetylene (HCCPh) afforded the corresponding [U(Tp^Me2)₂(OAr)] (Ar = C₆H₂-2,4,6-Me₃) (1), [U(Tp^Me2)₂(dmpz)] (2), [U(Tp^Me2)₂(η²-SC₅H₄N)] (3), and [U(Tp^Me2)₂(CCPh)] (4) compounds. Reaction of [U(Tp^Me2)₂(NR₂)] with Me₃SnCl or Me₃SiBr gave [U(Tp^Me2)₂Cl] (5) and [U(Tp^Me2)₂Br] (6), respectively, in high yield. The amido precursors failed to react with cyclopentadiene, but metathesis of [U(Tp^Me2)₂I] with NaCp yielded [U(κ³-Tp^Me2)(κ²-Tp^Me2)(η⁵-Cp)] (7). Thermolysis of 7 resulted in oxidation of the metal centre and redistribution of the ligands, giving [UCp₃(dmpz)] (8), pyrazabole (9) and [U(Tp^Me2)(dmpz)₃] (10). The complexes have been fully characterized by spectroscopic methods and the structures of 1, 2, and 5 were confirmed by X-ray crystallographic studies. In the solid state the complexes exhibit distorted pentagonal bipyramidal geometries.     

Electron paramagnetic resonance study of the reactions of tetrathiomolybdate with roussin salts and esters, and with some related iron nitrosyls

The tetrathiomolybdate ion [MoS₄]²⁻ reacts in DMF solution with Roussin esters Fe₂(SR)₂(NO)₄ (R = Me, Et, n-Pr, i-Pr, n-Bu,t-Bu, n-C₅H₁₁) to yield the paramagnetic iron nitrosyls [Fe(NO)₂(SR)₂]⁻ (1), [Fe(NO)₂(S₂MoS₂]⁻ (2) and [Fe(NO)(S₂MOS₂)₂]⁻ (3). The new complexes (2) and (3) have been characterized by EPR spectroscopy and the assignment to them of constitutions based respectively upon tetrahedral and square pyramidal iron is supported by EHMO calculations. Fe₂(SPh)₂(NO)₄ with [MoS₄]²⁻ yields only [Fe(NO)₂(SPh)₂]⁻, and preformed (3) reacts with PhS⁻ to give firstly EPR-silent species, and then [Fe(NO)₂(SPh)₂]⁻. The mononitrosyl (3) can also be formed by reaction of [MoS₄]²⁻ with [Fe₄S₃(NO)₇]⁻, Fe₄S₄(NO)₄, or Fe₂I₂(NO)₄.     

Synthesis, structure and hydrogenation catalytic activity of [Ru3(μ3,η-ampy)(μ,η:η-PhC=CHPh)(CO)6(PPh3) (Hampy = 2-amino-6-methylpyridine)

The compound [RU₃(μ₃,η²- -ampy)(μ₃η¹:η²-PhC=CHPh)(CO)₆(PPh₃)₂] (1) (ampy = 2-amino-6-methylpyridinate) has been prepared by reaction of [RU₃(η-H)(μ₃,η²- ampy) (μ,η¹:η²-PhC=CHPh)(CO)₇(PPh₃)] with triphenylphosphine at room temperature. However, the reaction of [RU₃(μ-H)(μ₃, η² -ampy)(CO)₇(PPh₃)₂] with diphenylacetylene requires a higher temperature (110°C) and does not give complex 1 but the phenyl derivative [RU₃(μ₃,η²-ampy)(μ,η ¹:η² -PhC=CHPh)(μ,-PPh₂)(Ph)(CO)₅(PPh₃)] (2). The thermolysis of complex 1 (110°C) also gives complex 2 quantitatively. Both 1 and 2 have been characterized by0 X-ray diffraction methods. Complex 1 is a catalyst precursor for the homogeneous hydrogenation of diphenylacetylene to a mixture of cis- and trans -stilbene under mild conditions (80°C, 1 atm. of H₂), although progressive deactivation of the catalytic species is observed. The dihydride [RU₃(μ-H)₂(μ ₃,η²-ampy)(μ,η¹:η²- PhC=CHPh)(CO)₅(PPh₃)₂] (3), which has been characterized spectroscopically, is an intermediate in the catalytic hydrogenation reaction.     

Arylkomplexe des typs trans-[Ir(Ar)(CO)(PPh3)2]

The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh₃)₂] (Ar = C₆H₅, C₆F₅, 2-C₆H₄CH₃, 3-C₆H₄CH₃, 4-C₆H₄CH₃, 2-C₆H₄OCH₃, 2,6-C₆H₃-(OCH₃)₂, 4-C₆H₄N(CH₃)₂, 3-C₆H₄Cl, 4-C₆H₄Cl, 4-C₆H₄Cl, 3-C₆H₄CF₃, 4-C₆H₄CF₃) are described, and the most important IR data as well as the ³¹P NMR parameters of these, without exception trans-planar, compounds are given.

Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O₂)(CO)(PPh₃)₂] (Ar = C₆H₅, 3-C₆H₄CH₃, 4-C₆H₄CH₃). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO₂ the similar irreversible addition compound [Ir(4-C₆H₄CH₃)-(SO₂)(CO)(PPh₃)₂] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed.

The first step of the reaction between [Ir(4-C₆H₄CH₃)(CO)(PPh₃)₂] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C₆-H₄CH₃)(CO)(PPh₃)₂]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature.     

Synthesis and X-ray crystal structures of [Ru4H4(CO) 11(PPh3)] and [Ru4−x IrxH2−x(CO) 12(PPh3) ] (x = 0 or 1)

Three tetranuclear clusters [Ru₄H₄(CO)₁₁(PPh₃)] (1), [Ru₄H₂(CO)₁₂(PPh₃)] (2) and [Ru₃IrH(CO)₁₂(PPh₃)] (3) were formed in the reaction of [Ir(CO)Cl(PPh₃)₂] and Na[Ru₃H(CO)₁₁] in tetrahydrofuran. Complexes 1–3 were characterized by IR and ¹H and ³¹P NMR, and the structure of the clusters was confirmed by single crystal X-ray analysis. In 2 and 3 one of the carbonyls bridges between two ruthenium atoms; otherwise the compounds contain only terminal carbonyls.     

Syntheses, X-ray structures, and reactions of ruthenium carbonyl complexes containing 1,1-dithiolates

Treatment of [Ru₂(CO)₄(MeCN)₆][BF₄]₂ or [Ru₂(CO)₄(μ-O₂CMe)₂(MeCN)₂] with uni-negative 1,1-dithiolate anions via potassium dimethyldithiocarbamate, sodium diethyldithiocarbamate, potassium tert-butylthioxanthate, and ammonium O,O′-diethylthiophosphate gives both monomeric and dimeric products of cis-[Ru(CO)₂(η²-(SS))₂] ((SS)⁻=Me₂NCS₂⁻ (1), Et₂NCS₂⁻ (2), ^tBuSCS₂⁻ (3), (EtO)₂PS₂⁻ (4)) and [Ru(CO)(η²-(Me₂NCS₂))(μ,η²-Me₂NCS₂)]₂ (5). The lightly stabilized MeCN ligands of [Ru₂(CO)₄(MeCN)₆][BF₄]₂ are replaced more readily than the bound acetate ligands of [Ru₂(CO)₄(μ-O₂CMe)₂(MeCN)₂] by thiolates to produce cis-[Ru(CO)₂(η²-(SS))₂] with less selectivity. Structures 1 and 5 were determined by X-ray crystallography. Although the two chelating dithiolates are cis to each other in 1, the dithiolates are trans to each other in each of the {Ru(CO)(η²-Me₂NCS₂)₂} fragment of 5. The dimeric product 5 can be prepared alternatively from the decarbonylation reaction of 1 with a suitable amount of Me₃NO in MeCN. However, the dimer [Ru(CO)(η²-Et₂NCS₂)(μ,η²-Et₂NCS₂)]₂ (6), prepared from the reaction of 2 with Me₃NO, has a structure different from 5. The spectral data of 6 probably indicate that the two chelating dithiolates are cis to each other in one {Ru(CO)(η²-Et₂NCS₂)₂}fragment but trans in the other. Both 5 and 6 react readily at ambient temperature with benzyl isocyanide to yield cis-[Ru(CO)(CNCH₂Ph)(η²-(SS))₂] ((SS)=Me₂NCS₂⁻ (7) and Et₂NCS₂⁻ (8)). A dimerization pathway for cis-[Ru(CO)₂(η²-(SS))₂] via decabonylation and isomerization is proposed.     

Optically active coordination compounds---XLVIII. Synthesis, resolution and interconversions of isomers of tris-salicylatocobaltate(III)

Stable aqueous solutions of the green ion [Co(sa1)₃]³⁻ (sa1 = dianion, C₆H₄( )(CO ), of salicylic acid, 2-hydroxybenzoic acid) are obtained from [Co(NH₃)₅ C1]C1₂ and an excess of salicylic acid. Several salts, [C][Co(sa1)₃] have been characterized, where C = [Co(NH₃)₆]³⁺ and [M(en)₃]³⁺ (M = Co or Rh, EN = 1,2-diamino-ethane). By using (+)-[Rh(en)₃]³⁺, optical resolution via less soluble diastereoisomeric salts has been achieved, and isomerization and racemization have been studied. Resolved tris-malonatocobaltate(III) has been used as a model. A novel thermochromism (77-293 K) in solid Δ(+)-[Rhen₃]Λ[Co(sa1)₃ is described.     

Reactions of transition-metal carbonyls with anhydrous HF

The reactions of a wide range of transition-metal carbonyls with anhydrous HF are described. In particular, Ru₃(CO)₁₂, Os₃(CO)₁₂ and Ir₄(CO)₁₂ give the solution stable [Ru₃(CO)₁₂H]⁺, [Ru(CO)₅H]⁺, [Os₃(CO)₁₂H]⁺, [Os(CO)₅H]⁺ and [Ir₄(CO)₁₂H₂]²⁺ respectively, which have been characterised by a combination of ¹H and ¹³C NMR spectroscopy.     

Group 4 metallacarboranes of constrained geometries derived from B(cage)- and C(cage)-silylamido-substituted carborane ligands: a synthetic and structural investigation

The reactions of RNHSi(Me)₂Cl (1, R=t-Bu; 2, R=2,6-(Me₂CH)₂C₆H₃) with the carborane ligands, nido-1-Na(C₄H₈O)-2,3-(SiMe₃)₂-2,3-C₂B₄H₅ (3) and Li[closo-1-R′-1,2-C₂B₁₀H₁₀] (4), produced two kinds of neutral ligand precursors, nido-5-[Si(Me)₂N(H)R]-2,3-(SiMe₃)₂-2,3-C₂B₄H₅, (5, R=t-Bu) and closo-1-R′-2-[Si(Me)₂N(H)R]-1,2-C₂B₁₀H₁₀ (6, R=t-Bu, R′=Ph; 7, R=2,6-(Me₂CH)₂C₆H₃, R′=H), in 85, 92, and 95% yields, respectively. Treatment of closo-2-[Si(Me)₂NH(2,6-(Me₂CH)₂C₆H₃)]-1,2-C₂B₁₀H₁₁ (7) with three equivalents of freshly cut sodium metal in the presence of naphthalene produced the corresponding cage-opened sodium salt of the “carbons apart” carborane trianion, [nido-3-{Si(Me)₂N(2,6-(Me₂CH)₂C₆H₃)}-1,3-C₂B₁₀H₁₁]³⁻ (8) in almost quantitative yield. The reaction of the trianion, 8, with anhydrous MCl₄ (M=Ti and Zr) in 1:1 molar ratio in dry tetrahydrofuran (THF) at −78 °C, resulted in the formation of the corresponding half-sandwich neutral d⁰-metallacarborane, closo-1-M[(Cl)(THF)_n]-2-[1′-η¹σ-N(2,6-(Me₂CH)₂C₆H₃)(Me)₂Si]-2,4-η⁶-C₂B₁₀H₁₁ (M=Ti (9), n=0; M=Zr (10), n=1) in 47 and 36% yields, respectively. All compounds were characterized by elemental analysis, ¹H-, ¹¹B-, and ¹³C-NMR spectra and IR spectra. The carborane ligand, 7, was also characterized by single crystal X-ray diffraction. Compound 7 crystallizes in the monoclinic space group P2₁/c with a=8.2357(19) Å, b=28.686(7) Å, c=9.921(2) Å; β=93.482(4)°; V=2339.5(9) ų, and Z=4. The final refinements of 7 converged at R=0.0736; wR=0.1494; GOF=1.372 for observed reflections.     

Isotopic exchange reactions between iron-sulphur-nitrosyl clusters and nitrite

The anion [Fe₄S₃(NO)₇]⁻ undergoes slow exchange with labelled nitrite [¹⁵NO₂]⁻ to yield a product [Fe₄S₃(¹⁴NO)(¹⁵NO)₆]⁻ in which complete isotopic exchange has occurred at the basal Fe(NO)₂ groups, but with no exchange at the apical Fe(NO) group. The neutral Fe₄S₄(NO)₄ reacts rapidly with [¹⁵NO₂⁻ to give fully exchanged [Fe₄S₃(¹⁵NO)₇]⁻, and it is proposed that the conversion proceeds by fragmentation, followed by complete isotopic exchange and rapid reassembly. The binuclear anion [Fe₂S₂(NO)₄]²⁻ also yields, with [¹⁵NO₂]²⁻ in CD₂Cl₂ solution, the fully exchanged [Fe₄S₃(¹⁵NO)₇]⁻, and a mechanism involving successive fragmentation, exchange and reassembly steps is proposed; however in aqueous solution, a clean exchange reaction occurs to give [Fe₂S₂(¹⁵NO)₄]²⁻. Neutral binuclear esters Fe₂(SR)₂(NO)₄ (R = Me, Et, or Ph) with [¹⁴NO₂]⁻ yield the mononuclear paramagnetic [Fe(¹⁴NO)₂(¹⁴NO₂)₂]⁻, and with [¹⁵NO₂]⁻ the analogous [Fe(¹⁵NO)₂(₁₅NO₂)₂]⁻.     

First examples of η- and η --- η-coordination in triphosphorus analogues of ferrocene. Crystal structure of the iron sandwich complex [Fe(η-C5H5) (η-C2R2P3)W (CO)5] (R = Bu)

Syntheses of the novel sandwich compounds [Fe(η⁵-C₅H₅)(η⁵-C₂R₂P₃)] and [Fe(η⁵-C₅H₅)(η⁵-C₂R₂P₃)W(CO)₅], (R = Bu^t), are described. The mode of attachment of the [W(CO)₅] fragment in the latter compound has been determined by NMR and single crystal X-ray diffraction studies.     

Titanium imido complexes containing 1,3,5-triazacyclohexane ligands

The syntheses of the 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane-supported imido complexes [M(NR)(R′₃tach)Cl₂] (M = Ti or Zr (NMR only); R = Bu^t or 2,6-C₆H₃Prⁱ₂; R′ = Me or Bu^t) are reported, along with that of the thermally robust dibenzyl derivative [Ti(NBu^t)(Me₃tach)(CH₂Ph)₂]. The tert-butylimido ligand in [Ti(NBu^t)(Me₃tach)Cl₂] undergoes exchange with ArNH₂ (Ar = 4-C₆H₄Me or 2,6-C₆H₄Me or 2,6-C₆H₃Prⁱ₂) to form the corresponding arylimides [Ti(NAr)(Me₃tach)Cl₂]. The Me₃tach ring in [Ti(NR)(Me₃tach)Cl₂] undergoes slow exchange with Bu^t₃tach or Me₃tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) to give the ring-exchanged products [Ti(NR)(Bu^t₃tach)Cl₂] and [Ti(NR)(Me₃tacn)Cl₂], respectively. The complexes [Ti(NR)(Me₃tach)X₂] (R = Bu^t or 2,6-C₆H₃Prⁱ₂; X = Cl or CH₂Ph) exhibit room-temperature dynamic NMR behaviour via an unusual trigonal twist of the facially coordinated Me₃tach ligand, and the activation parameters for these processes have been measured and are discussed. The X-ray structures of [Ti(NR)(Bu^t₃tach)Cl₂] (R = Bu^t or 2,6-C₆H₃Prⁱ₂) and [Ti(NBu^t)(Me₃tach)(X)₂] [X= Cl or CH₂Ph) are reported. Me₃tach and Bu^t₃tach = 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane, respectively.     

Attempts at stepwise reduction of the carbon-nitrogen triple bond of a nitrile at two metal centres: study of the reactivity of [(CO)(PPh3)2Re( (μ-NCHPh)Ru(PPh3) 2(PhCN)] towards tetrafluoroboric acid and dihydrogen

The reaction of [(CO)PPh₃)₂Re(μ-H)₂(μ-NCHPh)Ru(PPh₃)₂(PhCN)] (2) with HBF₄-Me₂O generates [(CO)PPh₃)₂Re(μ- H)₂(μ,η¹,η²HNCHPh)Ru(PPh₃)₂(PhCN)][BF₄] (3). Monitoring the reaction by NMR spectroscopy shows the intermediate formation of [(CO)(PPh₃)₂ HRe(μ-H)₂(μ-NCHPh)Ru(PPh₃)₂(PhCN)][BF₄] (4). Attempted reduction of the imine ligand by a nucleophile (H⁻ or CN⁻) failed, regenerating 2. Under dihydrogen at 50 atm, 3 is slowly transformed into [(CO)(PPh₃)₂HRe(μ-H)₃Ru(PPh₃)₂(PhCN)][BF₄] (5) with liberation of benzyl amine.     

Gezielte Synthese von Kohlenwasserstoff-verbrückten Komplexen. Nucleophile addition von Pentacarbonylrhenat und -manganat an π-gebundene Dien-, Cyclodien-, Trimethylenmethan-, Cycloheptatrienyl- und Alkin-Liganden

Pentacarbonyl-rhenate and -manganate react with the cationic complexes [cpMo(CO)₂(diene)]⁺, [cpMo(CO)₂(cyclopentadiene]⁺, [cpMo(CO)₂(cyclohexadiene)]⁺, [cpMo(CO)₂(trimethylenemethane]⁺, [(OC)₃Mo(η⁷-C₇H₇)]⁺, [cp(OC)-(Ph₃P)Mo(alkyne)]⁺ to give the corresponding heteronuclear hydrocarbon-bridged complexes.     

Synthese und reaktivität von dienylmetall-verbindungen : XXVII. Ein einfacher weg zur synthese von cyclopentadienylcobalt(III)-dikationen

CpCo(CO)₂ is oxidised by [Cp₂Fe]BF₄ (Cp = C₅H₅) in the presence of neutral ligands L to give the dications [CpCoL₃]²⁺ (L = SMe₂, S(n-C₄H₉)₂, PMe₃, C₅H₅N, MeCN; Me = CH₃). In [CpCo(SMe₂)₃]²⁺, sulfane ligands are substituted by neutral ligands L, L---L and L---L---L, to give the complexes [CpCoL₃]²⁺ (L = SeMe₂, TeMe₂, PMe₃, P(OMe)₃, AsMe₃, SbMe₃, t-C₄H₉NC, C₅H₅N, MeCN), [Cp-Co(L---L)SMe₂]²⁺ (L---L = R₂P(CH₂)_nPR₂, n = 1, 2, R = C₆H₅; bipyridine, o-phenanthroline, neocuproin) and [CpCo(L---L---L)]²⁺ (L---L---L = RP(CH₂CH₂PR₂)₂, R = C₆H₅). The dications react with iodide resulting in the monocations [CpCoL₂I]⁺ and [CpCo(L---L)I]⁺. Azacobaltocinium cations [CpCo(C₄R₂H₂N)]⁺ (R = H, CH₃) are obtained by reaction of [CpCo(SMe₂)₃]²⁺ with metal pyrrolides.