Carbonyl derivatives of phthalocyaninatoiron(II), especially those containing group VI axial donor atoms. Crystal and molecular structure of carbonyl(N,N-dimethylformamide)phthalocyaninatoiron(II) and mössbauer studies of some of the products

The carbonyl adduct of phthalocyaninatoiron(II), FePc, with N,N-dimethylformamide (DMF) as axial ligand, FePc(CO)DMF, was prepared by the reaction of iron carbonyls, Fe(CO)₅ or Fe₂(CO)₉, with o-phthaalonitrile in DMF as solvent. Several carbonyl adducts of FePc of general formula FePc (CO)L are reported, with L being a ligand with oxygen, sulphur and nitrogen donor atoms (L = tetrahydrofuran, H₂O, CH₃OH, dimethylsulphoxide, tetrahydrothiophene, ammonia, n-propylamine, diethylamine, triethylamine). The crystal and molecular structure of FePc(CO)DMF·DMF was investigaed by X-ray diffraction methods. The compound has a monoclinic unit cell and space group P2₁/n, a 9.86(1), b 17.35(3), c 19.79(4) », β 87.9(2)°, Z = 4, U 3383 »³, D₃ 1.458 g cm^?3. The iron atom is hexacoordinated to the four inner nitrogen atoms of the macrocyle, to carbon monoxide (Fe—C distance 1.72(2) ») and to DMF (Fe—O distance 2.07(1) »). The extra DMF occupies lattice sites. All of the compounds reported in this paper are substantially diamagnetic. Mössbauer spectra show typical isomer shift parameters for the bis-adducts and for the carbonyl adduct, substantially independent of the nature of the axial ligand. The quadrupole splitting parameter of the carbonyl adducts is strongly affected by the nature of the axial ligand.     

Synthesis of two complexes of cadmium(II) iodide with benzenecarbothioamide (BCTA): Crystal and molecular structure of [Cd(BCTA)2I2]

The reaction between CdI₂ and benzenecarbothioamide (BCTA) in ethanol produces crystalline [Cd(BCTA)₂I₂] but in 1,2-dichloroethane it yields [Cd(BCTA)I₂] in powder form. [Cd(BCTA)₂I₂] has been characterized by X-ray crystallography, and both complexes have also been identified by infrared spectra in the solid phase, ¹H NMR, and electrical conductivity studies in solution. The crystals of [Cd(BCTA)₂I₂] are monoclinic, space group P2₁/c, with a = 747.6(1) pm, b = 1958.7(13) pm, c = 1363.6(6) pm, β = 110.307(3)° and Z = 4. Least-squares refinement of the structure based on 4260 observations led to final discrepancy indices of R = 0.043 and R_w = 0.054. The geometry around the cadmium atom is slightly distorted from the tetrahedral. The BCTA is coordinated through the sulphur atom: CdI(1) = 277.2(1) pm, CdI(2) = 272.6(1) pm, CdS(1) = 256.7(3) pm, CdS(2) = 257.5(2) pm. The electrical conductivity studies and NMR and IR spectra are consistent with the structure found for [Cd(BCTA)₂I₂] and suggest a dimeric trans symmetric tetrahedral structure with halogen bridging (C_2h) for [Cd(BCTA)I₂].     

Ein (Phosphonioalkinyl)- und ein Acetyl(tetracarbonyl)eisen

A (Phosphonioalkinyl)- and an Acetyl(tetracarbonyl)iron From the reaction of 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , and Fe(CO)₅ {[bis(dimethylamino)phosphoryl-methyl]-bis(dimethylamino)phosphonioethinyl}(tetracarbonyl)iron, 4 , and {1,1,3,3-tetrakis(dimethylamino)-1,4-dihydro- 1λ⁵,3λ⁵-[1,3]diphosphetium-2-carbonyl}(tetracarbonyl)-iron, 5 , can be isolated as crystalline products. The nmr, mass and ir spectra of the two compounds as well crystal and molecular structures of 4 are reported. The bonding situation in compounds 4 and 5 are discussed in detail.     

Fast atom bombardment mass spectra of [(diars)Fe(CO)2(C(O)Me)(P-donor)]+ BF4− salts

Characteristic fast atom bombardment (FAB) mass spectra (8 keV, argon, glycerol matrix) have been obtained for an isostructural series of organometallic cations of the form cis,trans[(diars)Fe(CO)₂(C(O)Me)L]⁺ Bf₄ (L = phosphorus donor). The fast atom bombardment mass spectra (FABMS) obtained show relatively abundant fragments corresponding to the cationic portion of the complex [C⁺]. Extensive fragmentation also occurs via successive CO loss, phosphorus donor ligand cleavage, and ligand decomposition. Evidence for a rearrangement fragmentation corresponding to the process [Fe(C(O)Me)]⁺ → [FeMe]⁺ + CO is presented.     

The solid state vibrational spectra of pentacarbonyl-pyridine-molybdenum(0) complexes

The solid state i.r. and Raman spectra are presented for a number of Mo(o) compounds of the type Mo(CO)₅X (X: pyridine derivatives). The νCO, δMoCO, νMoC and νMoN fundamentals are assigned considering a C_4ν symmetry and the complete vibrational analysis is given for the pyridine and the pyridine-d₅ complexes. A linear relation between the lowest Raman νCO mode and the νMoN has been observed.     

Cumulative author index: Vol. 126(1977)–150(1978)

The synthesis of μ-[phenyl(dicyclohexylphosphonio)ethenidyl]-μ-(diphenylphosphido)hexacarbonyldiiron, Fe₂(CO)₆[CC(PCy₂H)Ph](PPh₂) via nucleophilic attack by dicyclohexylphosphine at the β-carbon atom of the σπ-acetylide in Fe₂(CO)₆(CCPh)(PPh₂) is described. This complex, which contains a one-carbon 3-electron bridging ligand has been characterised by microanalysis, infrared, mass, Mössbauer and ³¹P NMR spectroscopy and by a single crystal X-ray structure determination. Crystals are monoclinic, space group P2₁/c with a 10.932(3), b 8.983(2), c 38.644(6) Å, β 94.48(2)°. With four molecules per unit cell and a formula weight of 764.4, the calculated density of 1.342 g cm^?3 agrees with the measured value of 1.34 g cm^?3. The structure was solved by heavy atom methods and refined by least squares techniques with iron and phosphorus atoms having anisotropic thermal parameters, to R and R_w values of 0.068 and 0.075 respectively. In the binuclear molecule an ironiron bond of length 2.550(2) Å is bridged by a diphenylphosphido group and the carbon atom of an unusual dipolar ligand Cy₂(H)P⁺C(Ph)C^?. In the bridging one-carbon-3-electron ligand the coordinated carbon atom is trigonal and the atoms P(1), C(8), C(31), C(7) are virtually coplanar. Structural parameters are compared with those of other complexes containing bridging one-carbon, 3-electron and two-carbon, 3-electron ligands. Nucleophilic attack by phosphorus and nitrogen nucleophiles on σπ-acetylides appears to be a general route to these ligands.     

Pentacoordinate iron(III) porphyrin carboxylates: Synthesis,physicochemical characteristics and x-ray crystal structure of acetato(5, 10, 15, 20-tetraparatolylporphyrinato) iron(III)

Carboxylatoiron(III) porphyrins have been synthesised by the action of carboxylic acids on the [(por)Fe]₂O dimers. ¹H NMR and ESR data of the isolated products are in accordance with pentacoordinate high spin 5/2 ferric complexes, the iron atom being displaced out of the plane of the porphyrin ligand. IR spectra show ν(CO) and ν(CO) bands separated by 356–409 cm^?1. The magnitude of this separation suggests coordination between the metal centre and the carboxylate group via one oxygen atom. Magnetic susceptibility measurements from 5 to 120 K lead to the value of μ = 5.88 B.M.. The X-ray structure of acetato (5, 10, 15, 20-tetra p-tolyporphyrinato) iron(III) confirms the above deductions. (tp MePP) Fe(CO₂CH₃). 0.5 CH₃COOH crystallises in the I2/c space group with unit cell parameters a = 24.464(8), b = 9.332(3), c = 37.174(4) Å, β = 90.49(2)°, V = 8485 ų, D_c = 1.27 g · cm^?3 and Z = 8. The crystal structure was refined to a conventional R(F) = 0.0584 and R_w(F) = 0.0653 for 5132 unique reflections with F₀ > 3σ(F₀). The iron atom is pentacoordinated by the four nitrogen atoms and one oxygen atom of the acetate group. It lies at 0.520(1) Å out of the porphinato plane and 0.485(1) Å out of the four nitrogen plane. The FeO bond length is 1.898(4) Å.     

Cumulated double bond systems as ligands : V. Dialkylsulfurdiimine compounds M(CO)4(RNSNR) (M = Cr,Mo, W) and M(CO)5(RNSNR) (M = Cr,W); structural,spectroscopic and fluxional properties.

The preparation and properties are reported of M(CO)₄(RNSNR) (M = Cr, Mo, W; R = i-Pr, t-Bu), in which the ligand is bidentate and in the trans,trans configuration, and of M(CO)₅(RNSNR) (M = CR, W; R = Et, i-Pr) in which the sulfurdiimine is monodentate and in the cis,trans configuration. In both cases the ligand is linked to the metal atom via the N-atom(s). With M(CO)₅(MeNSNMe) a second isomer is found in which the sulfurdiimine is probably bonded via the S-atom to the metal. All the pentacarbonyl compounds are fluxional; this is attributed to a gliding movement of the metal atom along the NSN system.Both W(CO)₄(t-BuNSN-tBu) and W(CO)₅(MeNSNMe) show vibronic coupling of metal to ligand charge transfer transitions with sulfurdiimine vibrations, as shown with Resonance Raman, but only for W(CO)₅(MeNSNMe) also with the symmetric mode of the equatorial carbonyl groups. The metalsulfurdiimine bond appears to be weak for M(CO)₅(RNSNR), but strong for M(CO)₄(RNSNR).     

Synthesis of the pentacarbonyl(chalcocarbonyl)chromium(0) complexes,Cr(CO)5(CX) (X = S,Se)

The arene complexes, (η⁶-C₆H₆)Cr(CO)₂(CX) (X = S, Se), react with excess CO gas under pressure in tetrahydrofuran at about 60° C to produce the Cr(CO)₅(CX) complexes in high yield. The IR and NMR (¹³C and ¹⁷O) spectra of these complexes are in complete accord with the expected C_4v molecular symmetry. Like the analogous W(CO)₅(CS) complex, both compounds react with cyclohexylamine to give Cr(CO)₅(CNC₆H₁₁). However, while W(CO)₅(CS) undergoes stereospecific CO substitution with halide ions (Y^? to form trans-[W(CO)₄(CS)Y]^?, the two chromium chalcocarbonyl complexes apparently undergo both CO and CX substitution to afford mixtures of [Cr(CO)₅Y]^? and trans-[Cr(CO)₄(CX)Y]^?.     

Substituted benzeneseleninic acids as bidentate ligands. Synthesis and spectroscopic studies of manganese(II) and iron(II) complexes

The para- and meta-substituted seleninato anion, XC₆H₄SeO⁻₂, forms complexes with manganese(II) and iron(II) of the type [M(XC₆H₄SeO₂)₂(H₂O)₂], which have been shown to contain the bidentate ligand in seleninato-_O, O′ derivatives, the water molecules being coordinated to the metals. From the electronic absorption spectra and from the magnetic susceptibility data we have proposed for all the complexes a distorted octahedral D_4h symmetry. The structure of the anhydrous para- and meta-substituted benzeneseleninato complexes of manganese(II) and iron(II) have been investigated by means of electrical conductance measurements, spectral (electronic and i.r.) studies and magnetic susceptibility measurements. The anhydrous complexes are always of the seleninato-O, O′ type with the ligands tetrahedrally coordinated to the central atom. The wavelengths of the principal absorption peaks have been accounted for quantitatively in terms of the crystal field theory for manganese(II) derivatives. The nephelauxetic parameters are all indicative of an appreciable metal-ligand covalency.     

The crystal structure of bromotris(tetracarbonylcobalt)tin(IV)

Crystal of BrSn[Co(CO)₄]₃ are hexagonal, a = 10.20, c = 11.81 å, space group P6₃. The molecule comparises a central tin atom, surrounded tetrahedrally by the bromine atom and three Co(CO)₄ groups. The SnCo bond length is 2.60 å.     

Permetalloplumbanes: Preparation of [Pb{Co(CO)3(L)}4] and [Pb{Fe(CO)2(NO)(L)}4].: Complexes containing four transition metal to lead bonds (L = tertiary arsine,phosphine or phosphite).

The sole and unexpected products from the reactions of a variety of lead (II) and lead (IV) compounds with [Co₂(CO)₆(L)₂] complexes (L = tertiary arsine, phosphine, or phosphite) in refluxing benzene solution are the blue, air-stable percobaltoplumbanes [Pb{Co(CO)₃(L)}₄]. These have also been obtained from the reaction of Na[Co(CO)₃(L)] (L  PBu₃ⁿ) with lead (II) acetate which with Na[Fe(CO)₂(NO)(L)] forms the isoelectronic [Pb{Fe(CO)₂(NO)(L)}₄] [L  P(OPh)₃]. The IR spectra of the complexes in the v(CO) and v(NO) regions are consistent with tetrahedral PbCo₄ or PbFe₄ fragments, trigonal bipyramidal coordination about the cobalt or iron atoms and linear PbCoAs, PbCoP, or PbFeP systems. Unlike [Pb{Co(CO)₄}₄], our complexes do not dissociate to [Co(CO)₃(L)]^? or [Fe(CO)₂(NO)(L)]^? ions when dissolved in donor solvents.     

Reactions of Dicyclopentadienyltitanium(III) compounds with carbon monoxide

Reactions of Cp₂TiR (R = Cl, C₆F₅, C₆H₅, o-CH₃C₆H₄) with CO give two types of products: terminally coordinated adducts, Cp₂Ti(R)CO, and insertion products, Cp₂TiCOR, i.e. acyl compounds. The acyl ligand is η²-coordinated at the titanium atom. The preparations and properties of the compounds are described.     

Synthesis and electrochemistry of Group 6 tetracarbonyl (N,N′-bis(ferrocenylmethylene)ethylenediamine)metal(0) complexes

Thermal substitution reaction of Cr(CO)₄(η^2:2-1,5-cyclooctadiene), Mo(CO)₄(η^2:2-norbornadiene), and W(CO)₅(η²-bis(trimethylsilyl)ethyne) with N,N′-bis(ferrocenylmethylene)ethylenediamine (bfeda) yields M(CO)₄(bfeda) complexes which could be isolated from the reaction solution and characterized by elemental analysis, MS, IR, and NMR spectroscopy. In the case of tungsten, W(CO)₅(bfeda) is formed as intermediate and then undergoes the ring closure reaction yielding the ultimate product W(CO)₄(bfeda). The electrochemical behavior of the M(CO)₄(bfeda) complexes was studied by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in dichloromethane with tetrabutylammonium tetrafluoroborate as electrolyte. Constant potential electrolysis of the complexes was performed successively at their peak potentials at 0 °C in their CH₂Cl₂ solution and the electrolysis was followed by in situ recording the electronic absorption spectra in every 5 mC. In the electrolysis of Cr(CO)₄(bfeda), the central Cr(0) is oxidized first and electrolysis continues with oxidations of two ferrocenyl groups until the end of totally three moles of electron passage per mole of complex. In the electrolysis of Mo(CO)₄(bfeda) and W(CO)₄(bfeda) the first oxidation occurs on the central atom forming a short-lived species which undergoes an intramolecular one-electron transfer and is reduced back to M(0) while one of the ferrocene units is oxidized to the ferrocenium cation at the same time. This indicates that the electron is transferred from iron to the central metal atom.     

Synthesis and x-ray crystallographic characterization of (μ3-Bi)2Fe3(CO)9: A reformulation of Hieber's Bi2Fe5(CO)20

When [HFe(CO)₄]^? is treated first with NaBiO₃ and then dilute H₂SO₄, a complex mixture of neutral metal carbonyl clusters results, some of which can be extracted into petroleum ether. Upon prolonged standing the extract yields a precipitate which has been characterized by X-ray crystallography as Bi₂Fe₃(CO)₉.The complex Bi₂Fe₃(CO)₉ crystallizes in the centrosymmetric orthorhombic space group Cmcm (D_2h¹⁷; No. 63) with a 10.616(2) Å, b 13.458(3) Å, c 11.347(3) Å, V 1621.1(7) ų and Z = 4. Single-crystal X-ray diffraction data (Mo-K_α, 2θ = 4.5–55.0°) were collected on a Syntex P2₁ four-circle diffractometer and the structure was refined to R_F 5.4% and R_WF 4.5% for all 1039 independent data (R_F 4.5% and R_WF 4.5% for those 851 reflections with |F₀| > 3.0σ(|F₀|)). The molecule lies on a site of crystallographic C_2v symmetry and is disordered. The individual molecules have a trigonal bipyramidal Bi₂Fe₃ core with the bismuth atoms occupying the apical sites (BiFe 2.617(2)–2.643(2) Å, FeFe 2.735(5)–2.757(5) Å). Each iron atom is linked to three terminal carbonyl ligands and the molecule has approximate C_3h symmetry. The nine peripheral oxygen atoms are ordered and define a tricapped trigonal prism. The equatorial iron atoms are disordered with the two Fe₃ triangles mutually displaced by approximately 30°; the disordered ensemble has approximate D_3h symmetry.     

Kristall- und molekülstruktur einiger pentacarbonyl(organometallchalkogenid)chrom- und -wolfram-komplexe

The structures of the isostructural compounds [(CH₃)₃Sn]₂SCr(CO)₅, [(CH₃)₃Sn]₂SeW(CO)₅, [(CH₃)₃Ge]₂SW(C0)₅ and [(CH₃)₃Pb]₂SW(CO)₅ have been determined by single crystal X-ray analyses. The compounds crystallize in the monoclinic system, space group P2₁/n. The substitution of one carbonyl group of the corresponding metal hexacarbonyls by the organometal chalcogenide causes a distortion of the M(CO)₅ group. The metal—chalcogen bonds are single bonds without significant π-bond contributions. The coordination around the chalcogen atoms is nearly tetrahedral.     

Crystal and molecular structure at −35°C of (π-cyclobutadiene)dicobalt hexacarbonyl

The structure of cyclobutadienedicobalt hexacarbonyl, (C₄H₄)Co₂(CO)₆, has been determined by single crystal X-ray diffraction techniques with data gathered at ?35°C by counter methods. Crystals form as red prisms in orthorhombic space group Pnma, with lattice parameters (at ?35°C) a = 12.916(3), b = 10.353(2) and c = 9.118(3) Å for a unit cell with four molecules of (C₄H₄)Co₂(CO)₆. The molecules have rigorous C_s symmetry, with a π-cyclobutadiene ring bound to the Co atom of a Co(CO)₂ moiety which, in turn, is linked to a Co(CO)₄ fragment through the metal atoms. Apparently to decrease repulsion between the cyclobutadiene ring and the bulky Co(CO)₄ group, the four-membered ring is tilted, and as a consequence the CoC₄H₄ interaction is unsymmetrical (CoC(ring) = 1.980(3) to 2.048(4) Å). Full-matrix least-squares refinement of the structure has converged with a R index (on |F|) of 0.027 for 1539 symmetry-independent reflections with I_o > 2.0σ(I_o) within the Mo-K_α shell defined by 4° < 2θ < 60°.     

Complexes amines du rhodium(I) : I. Complexes du type chloro-monoamine cyclooctadiène- 1,5 rhodium(I) et leurs produits de réaction avec l''oxyde de carbone

The reaction of amines with [(RhClCod)₂] (Cod = 1,5-cyclooctadiene) gives monomeric compounds [RhCl(Am)Cod](Am = amine). Elementary analyses as well as IR and NMR spectra are consistent with their structure.On treatment with carbon monoxide at atmospheric pressure these compounds give a series of complexes, [RhCl(Am)(CO)₂], identified by elementary analyses and IR spectra.The thermolysis of [RhCl(Aam)(CO)₂] with Aam = allyamine gives [{RhCl(Aam)CO_n}] not perfectly isolated. The reaction of [{RhCl(CO)₂}₂] with 2-vinylpyridine leads to the same kind of compound [{RhCl(Vpy)CO_m}] with Vpy = 2 -vinylpyridine. This latter complex is identified by elementary analysis. The IR spectra of these two complexes show that the olefinic double bond of amines β,γ-insaturated interacts with a rhodium atom. Their properties are discussed.     

Reactions of collman complex with tin(IV) and germanium(IV) porphyris,formation of [tin(II) and germanium(II) porphyrins] tetracarbonyliron and crystal structure of [2,3,7,8,12,13,17,18-octaethylporphinato tin(II)] tetracarbonyliron

The action of Na₂Fe(CO)₄ with tin(IV) and germanium(IV) porphyrins affords metal(II) porphyrin complexes [(por)M(II)Fe(CO)₄] (por = porphyrinate, M - Sn(II) or Ge(II)). The molecular structure of [(oep)Sn(II)Fe(CO)₄] was solved by X-ray diffraction techniques. The molecular structure of [(oep)Sn(II)Fe(CO)₄] was solved by X-ray diffraction techniques : the Sn coordination is square pyramidal with the iron in axial position (Sn-Fe = 2.492(1)Å) whereas the Fe coordination is trigonal bipyramidal. Mössbauer parameters provide convincing evidence for the formal zero oxidation state of the iron atom.     

The unusual iron complex with a trimethylenemethane type ligand, (η5-cyclopentadienyldicarbonylmanganese)- (phenylmethylene)carbomethaneiron tricarbonyl [Cp(CO)2 MnC(CO)CHPh]Fe(CO)3

The binuclear complex with composition [Cp(CO)₂ MnC(CO)CHPh]Fe(CO)₃ is obtained by interaction of CpMn(CCHPh)(CO)₂ with Fe₂C0)₉. An X-ray study of this complex has shown that besides three carbonyl groups the iron atom is covalently bonded to four atoms, viz. the carbon of a phenylmethylene group, the carbon of a bridging CO group, the manganese atom and the central carbon of the organomanganese ligand lying just above iron. It seems to be the first example of a heteroatomic analogue of trimethylenemethane complexes.