Crystal structure of twinned (η5-C5(CH3)4CF3) (η5-C5(CH3)5)Ru

The substituted sandwich complex crystallizes in monoclinic space groupP2₁/m withZ=2. Twinning to the (001) direction with the special conditionc ^*/4a ^* = cos ^* causes systematic superposition of the reciprocal lattices of both domains and results in an apparent unit cell with double volume and the reflection condition (2h)kl, l=2n. The structure solution was obtained with the subset of intensity data for the predominant individuum and converged atR = 0.040,R _w =0.046 for 832 independent observations and 122 variables. The molecules show disorder with respect to the crystallographic mirror plane. The structure is closely related to that of decamethylruthenocene.     

Derivate des borols: VII. (η5-borol)rhodium-komplexe und nucleophiler abbau von μ-(η5-1-phenylborol)-bis[(η5-1-phenylborol)rhodium]

Dehydrogenating complexation of borolenes C₄H₆BR (R = Me, Ph) with [Rh(η²-C₂H₄)₂Cl]₂ gives the triple-decked complexes μ-L-(RhL)₂ (III) with L = η⁵-C₄H₄BR. Cyclopentadienide degradation of III gives the uncharged complexes CpRhL (IV) and the water-soluble salts Na[RhL₂] (Na⁺ · V) which are characterized as NMe₄⁺ (R = Me) and Cs⁺ salts (R = Ph). In CD₂Cl₂/CF₃CO₂D the complex CpRh(η⁵-C₄H₄BPh) shows fast exchange at the α-position to the boron at 0°C, thus providing the first evidence of an electrophilic substitution of an (η⁵-borole)metal complex. Protonation of V gives RhHL₂ (VII) as the first (η⁵-borole)metal hydrides. Various neutral nucleophiles effect a valence disproportionation of IIIb (R = Ph) with formation of the compounds [LRhY₃][RhL₂] (VIII) (Y = PMe₃), IX (Y = P(OMe)₃), and X (Y = CNBu^t). Cyanide degradation of IIIb in acetonitrile yields K₂[LRh(CN)₃], characterized as PPh₄⁺ salt (XII). Further degradation in aqueous solution provides the anion [C₄H₄B(CN)Ph]⁻ (XIII) isolated as the [CoCp₂]⁺ salt (XIV). Anion XIII constitutes the first Lewis-base adduct of a simple, i.e. C-unsubstituted borole.     

Synthese von Tricarbonyl-η5-cyclohexadienyl-wolframat und Tricarbonyl-η5-cyclohexadienyl-methyl-wolfram

η⁶-Arene-tricarbonyl-tungsten (arene = benzene (1a), toluene (1b), m-xylene (1C), P-xylene (1D), o-xylene (1E), mesitylene (1F)) yield with potassium-tri-sec-butylboranate correspondingly methyl-substituted tricarbonyl-η⁵-cyclohexadienyl-tungstates (2A–2F). Similarly 1A reacts with methyllithium to tricarbonyl-η⁵-anti-6-methylcyclohexadienyl-tungstate (4A). In THF 2A–2F and 4A are converted by methyliodide to tricarbonyl-μ⁵-cyclohexadienyl-tungsten (3A–3F) and tricarbonyl-η⁵-anti-6-methylcyclophexadienyl-methyl-tungsten (5A). The complexes were characterized by C, H elemental analyses and by IR and ¹H-NMR spectroscopy.     

Triphospha-Ferrocenes as Ligands. Crystal Structures of [Fe(η5-C5Me5)(η5-C2 TBu2P3)M(CO)5)], (M= Cr,MO, W) and the Novel ruthenium and Nickel Complexes [Fe(η5-C5Me5) (η5-C2 TBu2P3)Ru3(CO)9] and [Fe(η5-C5Me5)(η5-C2 tBu2P3)Ni(Co)2]2

Abstract

Syntheses and structures of penta- and hexaphosphorus analogues of ferrocene have been described recently¹. Unlike their simple ferrocene analogues, these complexes have further ligating potential towards other transition metal centres by virtue of the availability of the ring phosphorus lone-pair electrons that are not involved in the η⁵-coordination. We now describe the first examples of coordination compounds of the triphospha-ferrocene [Fe(η⁵-C₅Me₅) (η⁵-C₂ ^tBu₂P₃]. In the ruthenium complex [Fe(η⁵-C₅Me₅)(η⁵-C₂ ^tBu₂P₃) Ru₃(CO)₉] ² two adjacent phosphorus atoms of the η⁵-C₂ ^tBu₂P₃ ring are interlinked by a ruthenium carbonyl cluster in which all three ruthenium atoms interact with the phosphorus atoms. The tetrametallic nickel complex [Fe(η⁵-C₅Me₅)(η⁵-C₂ ^tBu₂P₃)Ni(CO)₂]₂ ³ represents the first example of intermolecular interlinkage of two phospha-ferrocene systems by two metal centres.     

Synthesis and structures of the η5-C5H5Cl(CO)2W-η1,η5-(PPh2)C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 and MeSi[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3]3 complexes

The metallation of the η⁵-C₅H₅(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex with BuⁿLi (THF, ?78 °C) followed by the treatment of the lithium derivative with Ph₂PCl afforded the η⁵-Ph₂PC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex. The reaction of the latter with η⁵-C₅H₅(CO)₃WCl in the presence of Me₃NO produced the trinuclear complex η⁵-C₅H₅Cl(CO)₂W-η¹,η⁵-(Ph₂P)C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃. The structure of the latter complex was established by IR, UV, and 1H and ³¹P NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl₃ with three equivalents of LiC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃ gave the hexanuclear complex MeSi[C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃]₃.     

Electron transfer in organometallic clusters: XIV. Crystal and electronic structures of the tricobalt carbon cluster (η5-C5H5)Fe[η5-C5H4-CCo3(CO)9] and the biscarbyne cluster (η5-C5H5)Fe[η5-C5H4CCo3(η5-C5H5)3CH]

The crystal and molecular structures of (η⁵-C₅H₅)Fe[η⁵--C₅H₄CCo₃(CO)₉] (1), Pna2₁, α 17.354, b 11.463, c 11.207 Å Z = 4, R = 0.053, R_w = 0.056 for 939 reflections (I>3σ(I)) at 293 K, and (η⁵-C₅H₅Fe[η⁵--C₅H₄CCo₃(η⁵C₅H₅)₃CH] (2), P2₁/n, a 13.807(9), b 11.254(4), c 13.991(9) Å, β 99.98(5)°, Z = 4, R = 0.033 and R_w = 0.033 for 3051 observed reflections (I>3σ(I)) at 180 K, have been determined by X-ray methods.The results provide a detailed characterisation of related tricobalt-carbon complexes directly bound to ferrocene residues. In 1 the ferrocenyl moiety tops the pyramidal CCo₃ cluster core, while in 2 the CCo₃C core is bipyramidal with a ferrocenyl substituent on one capping carbon atom and a hydrogen atom at the other. In both cases the ferrocenyl group is tilted towards one cobalt atom of the cluster core, a distortion believed to be the consequence of the non-degeneracy of the carbyne p(π) orbitals resulting from a cooperative π-interaction between the clusters and the ferrocenyl substituents.     

N-(η5-Cyclopentadienylvanadium)benzenesulfonamide

N-(⁵-Cyclopentadienylvanadium)benzenesulfonamide has been synthesized for the first time by treating benzenesulfonamide orN-(tributylstannyl)benzenesulfonamide with vanadocene.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2107–2109, December, 1993.     

[Li3DME][(η~5-C_5H_5)_3Nd(μ-H)Nd(η~5-C_5H_5)_3]的合成及其分子结构

标题配合物是以THF作溶剂,通过(C_5H_5)_2NdCl·ZLiCl和甲基萘钠的还原反应合成的。其晶体属单斜晶系,P 2/c空间群,晶胞参数α=9.235(2)A,b=11.695(2)A,c=20.810(3)A,β=92.88(1)°,Z=2。研究结果表明,标题配合物由相互不相联的〔Li3DME〕~ 和〔(η~5-C_5H_5)_3Nd(μ-H)Nd(η~5-C_5H_5)_3〕~-离子对组成。阳离子中,Li原子与由3个DME提供的6个O原子配位,形成八面体构型,Li—O平均键长为2.116A;阴离子中,2个Nd原子不直接键合,系通过桥H联接,Nd—H=2.19A。此外,每个Nd原子各有3个C_5H_5~-与之配位,Nd—C平均键长为2.812A。     

Coordination-unsaturated complexes of tris(cyclopentadienyl)samarium: Solvate (η5-C5H5)3Sm·OC4H8 and ionic salt [Li(Et2O)2][η5-C5H5)3Sm(μ-Cl)Sm(η5-C5H5)3]

X-ray structural analysis of a samarium triscyclopentadienyl complex, Cp₃Sm·OC₄H₈ (1), and a samarium ionic salt, [Li(Et₂O)₂][Cp₃Sm(-Cl)SmCp₃] (2), was carried out. In both compounds coordination saturation is achieved by coordination of the THF molecule (in1) or the Cl^– anion (in2) to the monomeric fragment Cp₃Sm. An unusual coordination of the Li⁺ cation was observed in complex2: it is bound to one of the ⁵-type cyclopentadienyl rings in addition to two ether molecules.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1129–1132, June, 1993.     

Darstellung und kristallstruktur von μ3-allyl-μ1-chlorobis(triphenylphosphin)dipalladium(I)

μ₃-Allyl-μ₁-chloro-bis(triphenylphosphine)dipalladium(I) was obtained by the reaction of (π-C₃H₅PdCl)₂ with P(C₆H₅)₃ and NaOCH₃. The X-ray structure analysis of the yellow air-stable crystals confirms the presence of a PdPd bond (2.623 Å) and a bridging μ₃-allyl group. The PdC distances to the terminal carbon atoms of the allyl group are 2.07(1) Å. The distances of the Pd atoms to the bridging chloride ion are 2.433(3) and 2.438(3) Å.     

Efficient Diastereoselective Synthesis of Chiral Diferrocenylphosphine‐diamines: X‐ray Crystal Structure of [(η5‐C5H5)Fe{(η5‐C5H3)PPh2CH(CH3) N(CH2)2(CH2)2NCH(CH3)PPh2 (η5‐C5H3)}Fe(η5‐C5H5)]

Abstract

Three novel chiral planar diferrocenylphosphine‐diamines 5 (a–c) were designed and synthesized starting with (s)‐(?)‐N,N‐dimethyl‐1‐ferrocenylethylamine‐1 [(S)‐1]. All new compounds were identified by ¹H NMR and MS. The structure of chiral diferrocenylphosphine‐diamine 5c was determined by X‐ray crystallography. Single crystal X‐ray diffraction analysis reveals that the molecular structure of compound 5c [(η⁵‐C₅H₅)Fe{(η⁵‐C₅H₃)PPh₂CH(CH₃) N(CH₂)₂(CH₂)₂NCH(CH₃)PPh₂‐(η⁵‐C₅H₃)}Fe(η⁵‐C₅H₅)] is enantiomerically pure and crystallizes in the noncentrosymmetric P2(1)2(1)2(1) space group; it maintains “Z” shape and contains a piperazine hexahydrate ring bridge. The piperazine ring adopts a favored chair conformation and the chiral center C₂₃ and C₂₉ substituents in S‐configuration.     

New access to (η(5)-cyclohexadienyl)Mn(CO)3 and cationic (η(6)-arene)Mn(CO)3 complexes by Suzuki-Miyaura reaction

First Suzuki-Miyaura coupling reactions applied to (η(5)-chloro-cyclohexadienyl)Mn(CO)3 complexes are described and lead to the syntheses of (η(5)-aryl-cyclohexadienyl)Mn(CO)3 and of cationic (η(6)-arene)Mn(CO)3 complexes after rearomatization. The structures of two of the new complexes have been investigated by X-ray diffraction study.     

Insertionsreaktionen von carbonylbis(η-cyclopentadienyl)hydridoniob mit heteroallenen

Carbonylbis(η-cyclopentadienyl)hydridoniobium, Cp₂NbH(CO) (I) reacts with various heteroallenes such as p-tolyl isothiocyanate, diphenyl ketene, diphenylvinyl-N-p-tolyl ketene-imine, and p-tolyl isocyanate to give insertion products.     

The mechanism of fluxionality of (1,2,7-η3-2-Me-benzyl)(η5-C5H5)Mo(CO)2

It is shown that (1,2,7-η³-2-Me-benzyl)(η⁵-C₅H₅)Mo(CO)₂ exits in solution as one isomer which is fluxional, probably via (7-η¹-2-Me-benzyl)((η⁵-C₅H₅)Mo(CO)₂, with ΔG^≠₃₇₀ = 23.6 ± 1.0 kcal mol⁻¹. In contrast, (1,2,7-η³-3-Me-benzyl)(η⁵-C₅H₅)Mo(CO)₂ exits as two isomers at −20°C, which undergo interconversion at room temperature with ΔG^≠ 15.7 kcal mol⁻¹. This dynamic process is an allyl rotation. It is probable that there is also a low energy [1,5]-sigmatropic shift.     

Ligand exchange reactions of the alkyluranium(III) complexes (η5-C5H5)3URLi

The Cp₃URLi compounds (Cp = η⁵-C₅H₅; R = Me, n-Bu, n-Pent) have been synthesized by reaction of CP₃U(THF) with 1 equivalent of RLi. Exchange of the R alkyl occurs on treatment with alkyllithium reagents or in hydrogenolysis in the presence of a terminal olefin. These reactions presumably involve the Cp₃U and Cp₂UR species which are in equilibrium with the Cp₃URLi complexes.     

Zur Darstellung von η5-Cyclopentadienyl(dicarbonyl)-[η2-diethylamino(methylthio)carben]wolfram durch Thiomethylierung von η5-Cyclopentadienyl(dicarbonyl)diethylaminocarbinwolfram

Dicarbonyl(η⁵-cyclopentadienyl)(diethylaminocarbyne)(tungsten reacts with dimethyl(methylthio)sulfonium tetrafluoroborate to form dicarbonyl(η⁵-cyclopentadienyl)[η²-diethylamino(methylthio)carbene]tungsten in high yields.     

Substitution and insertion reactions of (η5-C5H5)Cr(CO)3C2H5

The complex (η⁵-C₅H₅)Cr(CO)₃Cp42 H₅ has been made and its reactions with σ donor ligands L (L = (MeO)₃P and (EtO)₃P) and with SO₂ studied. The alkyl phosphites give compounds of the composition (η⁵-C₅H₅)Cr(CO)₂LC₂H₅, and sulfur dioxide gives the corresponding S-sulfinato (η⁵-C₅H₅)Cr(CO)₃SO₂C₂H₅.