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.     

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.     

Molecular structure of ansa-compound (η5-C5H4)CMe2(η5-C9H6)TiCl2

The structure of a new ansa compound, (⁵-C₅H₄)CMe₂(⁵-C₉H₆)TiCl₂ (1), was studied by X-ray analysis:a = 15.00(1),b =15.500(5),c = 13.032(4) Å, = 92.66°(4),V = 3025.1(1) ų, space groupP2₁/.,R = 0.038. The distorted tetrahedral coordination sphere of the Ti atom is formed by two Cl atoms and two -ligands. It was proposed that the angle () between theC-M direction and the line normal to M-Cp can be considered as one of the geometric parameters characteristic of the structure-properties correlation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 305–308, February, 1995.     

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.     

Conformational analysis and x-ray crystal structure of [(η5-C5H5)Fe(CO)(PPh3)CH2CH3]

The complex [(η⁵-C₅H₅)Fe(CO)(PPh₃)CH₂CH₃] is shown by ¹H NMR spectroscopy and an X-ray crystal structure analysis to adopt a single conformation with the methyl group residing between the cyclopentadienyl and carbon monoxide ligands.     

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.     

(η^5-C5H5)(η^5-C5H4R)TiCl2类化合物的新合成方法

本文报道了取代环戊二烯基负离子与[(η~5-C_5H_5)TiCl_2]_2O反应生成(η~5-C_5H_5)(η~5-C_5H_4R)·TiCl_2的新方法。研究了取代环戊二烯基负离子的空间位阻和(η~5-C_5H_5)TiCl_3,[(η~5-C_5H_5)TiCl_2]_2O的结构以及反应温度对产物产率的影响。合成了七个新的(η~5-C_5H_5)(η~5-C_5H_4R)TiCl_2类型的化合物及七个相应的二氟化合物。     

(η^5-C5H5)(η^5-C5H4R)TiCl2类化合物的新合成方法

本文报道了取代环戊二烯基负离子与[(η^5-C5H5)TiCl2]2O反应生成(η^5-C5H5)(η^5-C5H4R).TiCl2的新方法. 研究了取代环戊二烯基负离子的空间位阻和(η^5-C5H5)TiCl3, [(η^5-C5H5)TiCl2]2O的结构以及反应温度对产物产率的影响. 合成了七个新的(η^5-C5H5)(η^5C5H4R)TiCl2类型的化合物及七个相应的二氟化合物。     

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.     

The preparation of a series of ring-linked derivatives of [Fe2(η-C5H5)2(CO)2(μ-CO)2] starting from [Fe2η5,η5-C5H4CH(NMe3)CH(NMe2)C5H4}(CO)2(μ-CO)2]+ salts

The salts [Fe₂η⁵,η⁵-C₅H₄CH{NMe₃)CH(NMe₂)C₅H₄}(CO)₂(μ-CO)₂][X] (X = I or SO₃CF₃) are the synthetic precursors to a wide range of [Fe₂(η-C₅H₅)₂(CO)₂(μ-CO)₂] derivatives in which the two cyclopentadienyl ligands are joined by a two-carbon bridge.     

Cyclooctaselenadiazole: synthesis,decomposition pathway,and reaction with (η5-C5H5) Co(L)2 (L = C2H4, PPh3). Crystal and molecular structure of [(η5-C5H5)CO]2(μ2-η3,η2-C8H6Se)

Thermolysis of cyclooctaselenadiazole (2) yields only selenium-containing products. Compound 2 reacts with CpCo sources to give [(η⁵-C₅H₅)CO]₂(μ₂η³,η²-C₈H₆Se), a fluxional compound whose structure has been determined by X-Ray crystallography.     

Organometallic polymorphism. Synthesis and structural characterization of two forms of [Ru(η6-C6H6)(η6-C6H4(CH3)COOCH3)][BF4]2 and the phase transition in [Ru(η5-C5H5)(η6-C6H5OH)][PF6]

The synthesis and structural characterization of the complex [Ru(η⁶-C₆H₆)(η⁶-C₆H₄(CH₃)COOCH₃)] [BF₄]₂ (2) and of its precursor [Ru(η⁶-C₆H₄(CH₃)COOCH₃)Cl₂]₂ (1) are reported. Compound (2) has been characterized in two polymorphic modifications (2a and 2b) and the molecular organization in the solid state has been investigated. The complex [Ru(η⁵-C₅H₅)(η⁶-C₆H₅OH)][PF₆] (3) has also been investigated; it has been shown to possess a disorder similar to that observed in the high temperature phase of related systems such as [Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][PF₆].     

A convenient,one-step synthesis of the cationic η3-allyl-molybdenum complex [(η5-C5H5)2Mo(η3-C3H5)]+[p-CH3C6H4SO3]−

[(η⁵-C₅H₅)₂Mo(η³-C₃H₅)]⁺ [p-CH₃C₆H₄SO₃]⁻ is conveniently synthesized by the reaction of (η⁵-C₅H₅)₂MoH₂ with allyl alcohol in the presence of p-toluene sulfonic acid, the mechanism of which is explained by the electrophilic cleavage of the allylO bond of the coordinated allyl alcohol.     

Addition of boranes to (E)-(η5-C5H5)2Zr(CH=CHPh)Cl

In this study, the addition of boranes to (E)-(η⁵-C₅H₅)₂Zr(CH=CHPh)Cl (3) has been examined in order to investigate the regioselectivity of these ‘hydroboration’ reactions. We have found that these additions proceed with remarkable selectivity to give exclusive formation of a saturated organic molecule where one carbon atom has both the boron and the zirconium fragments. These reactions do not proceed via a conventional hydroboration reaction, but instead go through an initial transmetalation step to generate (E)-(η⁵-C₅H₅)₂Zr(H)Cl (1) and the corresponding alkenyl boron intermediate, whereupon subsequent hydrozirconation of this latter species gives the geminal products. An x-ray diffraction study has been conducted on gem-(η⁵-C₅H₅)₂Zr(CH(Bpin)CH₂Ph)Cl (pin = 1, 2-O₂C₂Me₄) (2). Crystals of 2 were orthorhombic with a = 18.545(3) Å, b = 15.713(3) Å, c = 16.157(3) Å in the space group Pccn. An x-ray diffraction study has also been conducted on the trinuclear zirconium oxide species (η⁵-C₅H₅)₂ZrO₂[ZrCl(η⁵-C₅H₅)₂]₂ (4). Crystals of 4 were orthorhombic with a = 13.6000(8) Å, b = 14.2252(8) Å, c = 17.6500(10) Å in the space group P2(1)2(1)2(1).      

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.     

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.     

Preparation and crystal structures of [μ-SbPh2]2[Mo(CO)2(η5-C5H5)]2·CHCl3 and SbPh[Fe(CO)2(η5-C5H5)]2

Antimony is reduced when [SbPh₂BrO]₂ is treated with Na[Mo(CO)₃(η⁵-C₅H₅)] to produce [μ-SbPh₂]₂[Mo(CO)₂(η⁵-C₅H₅)]₂. A structure determination shows diphenylstibido groups bridging between two Mo(CO)₂(η⁵-C₅H₅) moieties giving a central ‘butterfly’ shaped Sb₂Mo₂ ring. The cyclopentadiene rings are trans to each other and Mo–Sb and Sb–Sb separations are both short. An iron analogue could not be obtained from [SbPh₂BrO]₂ and Na[Fe(CO)₂(η⁵-C₅H₅)] but a mixture of SbPh[Fe(CO)₂(η⁵-C₅H₅)]₂ and SbPh₂[Fe(CO)₂(η⁵-C₅H₅)] was obtained using SbPh₂Cl. An X-ray structure for SbPh[Fe(CO)₂(η⁵-C₅H₅)]₂ shows an open stibinidine structure.     

Five- and six-membered palladacycles derived from [(η5-C5H5)Fe{(η5-C5H4)-CH=N-(C6H4-2-C6H5)}]

The reaction of the novel ferrocenyl Schiff base: [(η⁵-C₅H₅)Fe{(η⁵-C₅H₄)-CH=N-(C₆H₄-2-C₆H₅)}] (1) with Na₂[PdCl₄] and Na(CH₃COO)·3H₂O in a 1:1:1 molar ratio in methanol is reported. In this reaction two different di-μ-chloro-bridged cyclopalladated complexes: [Pd{[(η⁵-C₅H₃)-CH=N-(C₆H₄-2-C₆H₅)]Fe(η⁵-C₅H₅)}(μ-Cl)]₂ (2a) and [Pd{[(C₆H₄-2-C₆H₄)-N=CH-(η⁵-C₅H₄)]Fe(η⁵-C₅H₅)}(μ-Cl)]₂ (2b) can be formed depending on the experimental conditions. Compounds 2a and 2b, which differ in the nature of the metallated carbon atom (C_{sp²,ferrocene} or C_{sp²,biphenyl}, respectively), undergo cleavage of the ‘Pd(μ-Cl)₂Pd’ bridges in the presence of thallium (I) acetylacetonate, deuterated pyridine or triphenylphosphine giving the monomeric derivatives: [Pd(C^∧N)(acac)] (3a, 3b) and [Pd(C^∧N)Cl(L)] {with L=py- d₅(4a, 4b), PPh₃(5a, 5b)}. The reactions of 2 with 1,2-bis(diphenylphosphino)ethane (dppe) reveal that the two isomers (2a and 2b) exhibit different reactivity versus dppe. These results have been interpreted on the basis of steric effects.     

Self-recognition by the iron chiral auxiliary [(η5-C5H5)Fe(CO)(PPh3] in the formation of (RR,SS)-[(η5-C5H5)FE(CO)(PPh3)COCH2]2CH2

Complete self-recognition of chirality is observed in the Michael addition of the enolate derived from R,S-[η⁵-C₅H₅Fe(CO)(PPh₃-COCH₃] to the acryloyl complex R,S-[(η⁵-C₅H₅Fe(CO)(PPh₃)-COCHCH₂)] to generate exclusively the single diastereoisomer of the glutaroyl complex RR,SS-[(η⁵-C₅H₅)Fe(CO)(PPh₃)COCH₂]₂CH₂.