Vinylidene complexes of transition metals : III. Derivatives of cyclopentadienyltricarbonyl rhenium with phenylvinylidene ligands. Crystal and molecular structure of Cp(CO)2Re[CC(Ph)C(Ph)CH2]Re(CO)2Cp

The novel complexes CpRe(CCHPh)(CO)₂ and Cp₂Re₂(μ-CCHPh)(CO)₄ containing a terminal and a bridging phenylvinylidene ligand respectively and the binuclear complex Cp(CO)₂Re[CC(Ph)C(Ph)CH₂]Re(CO)₂Cp were obtained in the reaction of CpRe(CO)₃ with PhCCH.According to an X-ray study of the latter complex the unusual bridging ligand is η¹-bonded to one Re atom and η²-bonded to the other.     

Raman and infrared spectroscopic investigation of alkyl derivatives of arsenic acid: Part VI. On the AsO-bond - calculation of force constants and vibrational energy distribution in compounds of the type RAsO3X2 And R2A

Normal coordinate analyses and force constant calculations were carried out using frequencies of infrared and Raman-spectra of the molecules and ions RAsO₃^2?, RAs(O)(OR)₂, RAs(O)(OH)₂, RAs(OH)O₂^?, RzAsO₂^?, R₂As(O)OH, and [R'₂As(OH)₂]⁺ (R = CH₃, R' = C₂H₅). Comparing bond orders of the AsO bond with those in corresponding phosphorus, selenium and sulphur compounds, we found influences of the electron deficiency effect and of bond polarity.     

Chemistry of vinylidene complexes: IV. Synthesis and the crystal and molecular structure of (η5-C5H5)MnOs3(μ2-CHCHPh)(μ-H)(μ-CO)(CO)11, an unusual heterometallic cluster

By the reaction of Cp(CO)₂MnCCHPh (I) with H₂Os₃(CO)₁₀ (II) the tetranuclear mixed-metal complex CpMnOs₃(μ₂-CHCHPh)(μ-H)(μ-CO)(CO)₁₁ (III) was prepared. An X-ray study of the structure of III showed that it is a spiked, tetranuclear cluster with the Mn atom linked to one of the vertices of the osmium triangle; the MnOs bond is bridged by CO and CHCHPh groups, the latter being σ-bonded to Os and η²-coordinated by Mn. In the course of the formation of III, hydrogenation and n-π rearrangement of the initial phenylvinylidene ligand take place. In solution, complex III readily eliminates the [CpMn(CO)₂] fragment to give triosmium clusters containing unsaturated organic ligands: HOs₃(μ₂-CHCHPh)(CO)₁₀, H₂Os₃(μ₃-CHCPh)(CO)₉, and H₂Os₃(μ₃-CCHPh)(CO)₉.     

Reaction of alkenyl carbonyl ruthenium(II) complexes with t-butyl isocyanide. Synthesis of η1-acylruthenium(II) complexes by intramolecular CO insertion

Reaction of Ru(CO)Cl(CHCHR)(PPh₃)₂ or Ru(CO)Cl(CHCHR)(PPh₃)₂L (L = py, Me₂Hpz) with 1 equivalent of t-butyl isocyanide gives the alkenyl derivatives Ru(CO)Cl(CHCHR)(PPh₃)₂(t-BuNC). When an excess of isocyanide is used, further reaction results in intramolecular CO insertion to yield η¹-acyl complexes [Ru(COCHCHR) (t-BuNC)₃(PPh₃)₂]Cl. Related complexes were obtained from [Ru(CO)(CHCHR)(MeCN)₂(PPh₃)₂]PF₆ and an excess of isocyanide.     

Vinyliden-Übergangsmetallkomplexe: II. Die Protonierung der Vinyliden-Komplexe C5H5Rh(CCHR)(PPri3) und ihre stufenweise Umwandlung in Vinyl- und α-Halogenalkyl-Rhodiumverbindungen

The protonation ofC₅H₅Rh(CCH₂)(PPrⁱ₃) (I) by CF₃CO₂H, HCl and HI gives the vinylrhodium compounds C₅H₅Rh(CHCH₂)(PPrⁱ₃)X (II-IV). The reaction of III (X = Cl) and IV (X = I) with a second molecule of HCl leads to the formation of the α-chloroethyl complexes C₅H₅Rh(CHClCH₃)(PPrⁱ₃)X (VII, VIII). The stereochemistry of these products allows us to propose a mechanism for HCl addition to the CC double bond of the vinyl ligand. C₅H₅Rh(CCHPh)(PPrⁱ₃) (XII) reacts with CF₃CO₂H and HI to give the kinetically preferred compounds C₅H₅Rh(Z-CHCHPh)(PPrⁱ₃)X (XIVa, XVa) of which XIVa (X = CF₃CO₂) in4bpolar solvents rearranges smoothly to form the thermodynamically more stable E isomer C₅H₅Rh(E-CHCHPh)(PPrⁱ₃)OCOCF₃ (XIVb). C₅H₅Rh(E-CHCHPh)(PPrⁱ₃)I (XVb) is obtained from XIVb and NaI. The protonation reactions of C₅H₅Rh(CCHMe)(PPrⁱ₃) (XIII) with CF₃CO₂H, HCl and HI always produce mixtures of isomers of the complexes C₅H₅Rh(CHCHMe)(PPrⁱ₃)X (XVI-XVIII). The ratio of Z to E isomers (≈ 62/38) is not dependent on the anion X and is also not influenced by the polarity of the solvent.     

Zur reaktion von metall-koordiniertem kohlenmonoxid mit yliden: XI. Einige neuartige η1-vinyl-komplexe des eisens durch deprotonierung kationischer carbenkomplexe mit trimethyl(methylen)phosphoran

Novel η¹-vinyl complexes of the type Cp(CO)(L)FeC(OMe)C(R)R′ (R = R′ = H, Me; R = H, R′ = Me; L = Me₃P, Ph₃P) are obtainied via methylation of the acyl complexes Cp(CO)(L)FeC(O)R (R = Me, Et, i-Pr) with MeOSO₂F and subsequent deprotonation of the resulting carbene complexes [Cp(CO)(L)FeC(OMe)R]SO₃F with the phosphorus ylide Me₃PCH₂. The same procedure can be applied for the synthesis of the pentamethylcyclopentadienyl derivative C₅Me₅(CO)(Me₃P)FeC(OMe)CH₂, while treatment of the hydroxy or siloxy carbene complexes [Cp(CO)(L)FeC(OR)Me]X (R = H, Me₃Si; X = SO₃CF₃) with Me₃CH₂ results in the transfer of the oxygen bound electrophile to the ylidic carbon. Some remarkable spectroscopic properties of the new complexes are reported.     

Synthèse de complexes du tungstène,du chrome et du rhénium contenant un ligand 1,4-bidenté carbéne-alcéne

A general synthesis of alkene-carbene complexes of tungsten, chromium and rhenium, containing a six-membered ring system, is outlined and the crystal structure of two new complexes of this type, (CO)₄WC(OEt)(CH)(η²-CH₂CHCH₂) (CH₂CHCH₂) and (CO)₉Re₂(OCH₂CH₃(CH₂(CH₂(CH₂CHCH₂), is described.     

Vinylidene complexes of transition metals : IV. The transfer of the phenylvinylidene ligand from manganese to rhenium. the novel binuclear complex Cp2MnRe(μ-CCHPh)(CO)4

The novel complex Cp₂MnRe(μ-CCHPh)(CO)₄ (I) containing the bridging phenylvinylidene ligand and MnRe bond was obtained in the reaction of CpMn(CCHPh)(CO)₂ with CpRe(CO)₂·THF. Complex I turns into CpRe(CCHPh)(CO)₂ under normal conditions. This is the first example of the transfer of the vinylidene ligand from one transition metal to another.     

Reactions of nitrilium triflate salts with trans-[IrCl(CO)(PPh3)2

Low yields of the ionic carbene complexes [Ir(RCNHMe)Cl(CO)(PPh₃)₂-(O₃SCF₃)]O₃SCF₃]O₃SCF₃ (R  Ph or PhCH₂) have been isolated from the reactions of trans-[IrCl(CO)(PPh₃)₂] with the nitrilium triflate salts, [RCNMe]O₃SCF₃. The major products from these, and the similar reactions of the nitrilium salts where R  Me or Bu^t, are amorphous, yellow complexes [Ir(RCNHMe)Cl(CO)(PPh₃)₂O₃SCF₃.     

The synthesis of thionitrosodimethylamine (Me2NNS) complexes of ruthenium,osmium, and iridium

Neutral hydrido complexes [ML]ClH(PPh₃)₃ ([ML] = Ru(CO), Os(CO) and Ir(Cl)] react with thionitrosodimethylamine, Me₂NNS, to give [ML]ClH-(SNNMe₂)(PPh₃)₂ with H trans to Me₂NNS, while the hydrido cations cis,trans-[[ML]H(SNNMe₂)₂(PPh₃)₂]⁺ are obtained from Me₂NNS and [Ru(NCMe)₂(CO)-(PPh₃)₂]⁺, [OsH(OH₂)(CO)(PPh₃)₃]⁺ and [IrClH(NCMe)₂(PPh₃)₂]⁺, respectively. The coordinatively unsaturated aryl complexes [ML′]Cl(p-tolyl)(PPh₃)₂ ([ML′]Ru(CO), Os(CO) and Os(CS)) coordinate one molecule of Me₂NNS to give [ML′]Cl(p-tolyl)(SNNMe₂)(PPh₃)₂, the chloride ligands of which are labile. Spectroscopic data suggest that in all these complexes the Me₂NNS ligand adopts a η¹(S) coordination mode.     

Isocyanide insertion into platinumoxygen bonds

The reaction of isocyanides, CNR, with hydroxy- and methoxy-alkyl complexes of platinum(II), PtOH(R)(Ph₂ PCHCHPPh₂)_and PtOCH₃(R)(Ph₂PCHCHPPh₂) (R  CF₃, CH₂ CN) affords insertion products Pt(CONHR)(R)(Ph₂PCHCHPPh₂) and Pt[C(OCH₃)NR] (R)(Ph₂PCHCHPPh₂) containing the carboxamido and imidoyl moiety, respectively.     

Syntheses of σ-cyclobut-1-en-3-onyl complexes by cycloaddition of ketenes to some transition metal alkynyl complexes

Reactions of ketenes (R¹R²CCO) with (η⁵-C₅H₅)Ni(PPh₃)CCR (I) and (η⁵-C₅H₅)Fe(CO)(L)CCR (III, L = CO and PPh₃) give σ-cyclobut-1-en-3-onyl complexes, {(η⁵-C₅H₅)Ni(PPh₃)$\text{CC(R)COC}$}R¹R² (VI) and (η⁵-C₅H₅)Fe(CO)(L)$\text{CC(R)COC}$R¹R² (IX)}, (2 + 2) cycloaddition products, in good yields. The σ-cyclobutenonyl complexes also can be prepared by the reaction of I and III with acyl chlorides in the presence of triethylamine.     

η-C5H5(CO)LFe-substituted imidates of acrylic acid. Synthesis and structure

Ethylation of Cp(CO)₂FeCHCHCONR₂ (I) yields the imidates [Cp(CO)₂FeCHCHC(OEt)NR₂]⁺X^? (II). A photochemical reaction between I and PPh₃ yields Cp(CO)(PPh₃)FeCHCHCHCONR₂ (III) from which the corresponding imidates (IV) can be obtained.Spectral data suggest that the positive charge in II and IV is localized mainly at the imidate group and that the participation of the Cp(CO)LFe substituent in the stabilization of the positive charge is insignificant, particularly in the case of cations lI.This conclusion is confirmed by X-ray analysis of IIb. Determination of the exact structure of IIb also reveals the absence of a direct interaction between the metal and the cationic center even though the complex has cis geometry. A reaction between Ic and Fe₂(CO)₉ yields a binuclear complex (IV). The initial complexes I were obtained by substitution of the anion [CpFe(CO)₂]^? for chlorine in ClCHCHCONR₂. These reactions are stereospecific.     

Complexation d'iminopyridines par le sel de zeise: voie d'access a des conjugues estradiol-cis-dichloro platine. Etude structure du complexe cis-PtCl2[C5H4NCH2NC(CH3)C6H4OH],H2O

In order to synthesize penta- and hexa-gonal platinum(II) metallocycles, bidentate ligands such as iminopyridines (L) have been prepared and characterized. The (2-pyridyl)CHNR¹ and (2-pyridyl)CH₂NCR¹R² ligands react with Zeise's salt to afford directly the pentagonal chelates PtCl₂L. Their structure and the cis-stereo-chemistry were shown by the usual spectroscopic methods and for cis-PtCl₂[C₅H₄NCH₂NC(CH₃)C₆H₄OH],H₂O by an X-ray diffraction study. On the other hand, the (2-pyridyl)(CH₂)₂NCR¹R² ligands do not afford the expected hexagonal metallocycles; instead, after complexation at the nitrogen atom of the imine they give rise to the (2-pyridyl)ethylamine complex formed after hydrolysis of the coordinated ligands. Complexes trans-[ethylene][(2-pyridyl)(CH₂)₂NCR¹R²]PtCl₂ represent when R¹ is estradiol a model for “cytotoxic with delayed activity”.     

Hydride-phosphoniodithiocarboxylate/ phosphonium-betaine isomerism in Cy3PCS2 complexes of ruthenium

Reaction of Cy₃PCS₂ (Cy = cyclohexyl) with the hydrido complexes [RuClH(CA)(PPh₃)₃] (A  O, S), [RuH(CO)(NCMe)₂(PPh₃)₂]⁺, and [RuH(OClO₃)(CO)(CN^tBu)(PPh₃)₂] leads to the complex cations [RuH(CA)(PPh₃)₂(η²-S₂CPCy₃)]⁺, [Ru(η²-S₂CHPCy₃)(CO) (PPh₃)₂]⁺, [RuH(η¹-S₂CPCy₃)(CO)(CN^tBu)(PPh₃)₂]⁺. The σ-vinyl complex [Ru(CHCHC₆H₄Me-4)Cl(CO)(PPh₃)₂] reacts with Cy₃PCS₂ to give the cationic complex [Ru(CHCHC₆H₄Me-4) (CO)(PPh₃)₂(η²-S₂CPCy₃)]⁺, but this complex is not formed by hydroruthenation of HCCC₆H₄Me-4 by [RuH(CO)(PPh₃)₂(η²-S₂CPCy₃)]⁺. The inter-relationships between the above complexes are discussed.     

1-Alkoxy-2-azaallenyl-komplexe von chrom und wolfram

The successive reaction of (CO)₆M with Na[NCR₂¹] and [Et₃O]BF₄ yields (CO)₅M[C(NCR₂¹)OEt] (II: M = Cr; III: M = W; CR₂¹ = C(C₆H₄Br-p)₂ (a), CPh₂ (b), C(C₆H₄OMe-p)₂ (c), C(C₆H₄)₂O (d), CBu₂^tt (e)). Hexacarbonyltungsten, (CO)₆W, reacts with Na[NCPh₂] and MeOSO₂F to give (CO)₅W[C(NCPh₂) OMe] (IV). X-Ray analysis of IIe shows that: (1) the CNC fragment is almost linear (171.7°); (2) the two NC bond lengths are equal within experimental error; and (3) the O,C,Cr,N plane is perpendicular to the C(Me₃),C,N,C(Me₃) plane (90.0°). Therefore compounds II–IV are best described as 1-alkoxy-2-azaallenyl complexes.     

Synthesis and crystal structure of a heterodinuclear complex with a bridged ethenyl ligand FeCo(CO)7(μ-CH=CPhH)

[Fe₂(CO)₆(μ-CO)(μ-CHCPhH)]⁻ reacts with Co₂(CO)₈ at room temperature to give the neutral heterodinuclear complex FeCo(CO)₇(μ-CHCPhH), which has been characterized by elemental analysis and spectroscopic (mass, IR and ¹H NMR) methods and by determination of its structure by X-ray diffraction.     

Dicyclopentadienyl-niobium(iii) and -niobium(iv) complexes

The reduction of (η-C₅H₅)₂NbCl₂ (I) under various conditions gives the dimer (η-C₅H₅)₄Nb₂Cl₃ (II) containing niobium(III) and niobium(IV). Reaction of II with AgClO₄ gives [(η-C₅H₅)₄Nb₂Cl₂]⁺ ClO₄^- (III). FeCl₃ and (C₆F₅)₂ TlBr displace I from II to give (η-C₅H₅)₂Nb(μ-Cl)(μ-X)MY₂, where MFe, XYCl(IV) and MTl, XBr, YC₆F₅ (V). Reactions of I with metal halides MXY₂ give (η-C₅H₅)₂ClNb(μ-Cl)MXY₂ where XYCl, MAl (VI), Fe (VII), Tl (VIII) and XBr, YC₆F₅, MTl (IX). The chemical behaviour of all these compounds is described.     

Inorganic Syntheses,Volume XXI : edited by J.P. Fackler,Jr., Wiley-Interscience,New York, 1982, xvii + 215 pages, £29.25.

The 1/1 reaction of Et₂Zn with N-t-butyliminopropanone (t-BuNC(H)C(Me)O) leads to quantitative formation of dinuclear [EtZ$\text{n(Et)(t-Bu)NC(H)=C(Me)O}$]₂ via ethyl transfer within the unstable Et₂Zn(t-BuNC(H)?C(Me)O) complex. An X-ray structure determination has shown the product to have a dinuclear structure involving a N,O-chelate bonded [Et(t-Bu)NC(H)C(Me)O]^? mono-anionic ligand and a central four membered Zn₂O₂ ring formed by intermolecular ZnO coordination. Hydrolysis of this zinc complex gives a quantitative yield of N-t-butyl-N-ethylamino propanone, which upon reaction with Et₂Zn reforms the dinuclear zinc complex.     

The reaction of trihydrobistriphenylphosphine iridium IrH3(PPh3)2 with diazonium salts

The reaction of IrH₃(PPh₃)₂ with p-substituted aryldiazonium salts gives the compounds [IrH₂(NHNC₆H₄R)(PPh₃)₂]⁺BF₄^- at low temperature (-10°C) and the o-metalated complexes [I$\text{rH(NHN}$C₆H₃R)(PPh₃)₂]⁺BF₄^- (R  F, OCH₃) at 40–50°C. The reactions of the o-metalated complexes with CO, PPh₃, NaI and HCl have been studied.