Multiple ligand transfer reaction between [CpRu(L)(AN)2][PF6] (L=AN, CO, P(OMe)3; AN=acetonitrile) and CpFe(CO)L′X (L′=CO, PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Cl, Br, I)

Treatment of ruthenium complexes [CpRu(AN)₃][PF₆] (1a) (AN=acetonitrile) with iron complexes CpFe(CO)₂X (2a–2c) (X=Cl, Br, I) and CpFe(CO)L′X (6a–6g) (L′=PMe₃, PMe₂Ph, PMePh₂, PPh₃, P(OPh)₃; X=Cl, Br, I) in refluxing CH₂Cl₂ for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)₂X (3a–3c) (X=Cl, Br, I) and CpRu(CO)L′X (7a–7g) (L′=PMe₃, PMe₂Ph, PMePh₂, PPh₃, P(OPh)₃; X=Br, I), respectively. Similar reaction of [CpRu(L)(AN)₂][PF₆] (1b: L=CO, 1c: P(OMe)₃) causes double ligand transfer to yield complexes 3a–3c and 7a–7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)]₂ was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH₂Cl₂ at room temperature to give 3a, and transforms into 7a by the reaction with PMe₃.     

The reactions of some protected and unprotected monosaccharides with M(NO){HB(3,5-Me2C3HN2)3}X2 (M = Mo, X = Cl, Br, I; M = W, X = Cl)

The reactions between [M(NO){HB(3,5-Me₂C₃HN₂)₃}X₂] (M = Mo, X = Cl, Br, I; M = W, X = Cl) and the monosaccharides 2,3:4,5-di-O-iso-propylidene-β- -fructopyranose, 2,3:5,6-di-O-isopropylidene-- -mannofuranose, methyl-- -glucopyranoside and -(+)-mannofuranose have been investigated and the complexes [M(NO){HB(3,5- Me₂C₃HN₂)₃}X(OR)] (M = Mo, X = Cl, Br, I; M = W, X = Cl; ROH = 2,3:4,5-di-O- isopropylidene-β- -fructopyranose) have been isolated as mixtures of diastereoisomers.     

Spectroscopic and structural studies on metal halide complexes of 4-vinylpyridine

Fourier transform infrared spectra (4000–400 cm⁻¹) are reported for metal(II) halide 4-vinlypridine complexes of the following stoichiometries: [MX₂(4-vipy]_n (n=4, M=Ni, X=Cl or Br; n=2, M=Cd, X=Cl, Br or I) and assignment are given for all the observed bands. These spectra were compared with X-ray powder diffraction patterns of complexes. It is shown that the proposed structures for these complexes derived from FTIR spectra are consistent with the X-ray powder diffraction measurements and the elemental analysis results. Coordination effect on 4-vinylpyridine has also been investigated.     

Copper(II), nickel(II) and cobalt(II) complexes of 4-cyanobenzonic acid: syntheses, crystal structures and spectral properties

Three new metal complexes, Cu(4-Hcba)₂(4-cba)₂(Py)₂ (4-Hcba=4-cyanobenzoic acid) 1 and M[H(4-cba)₂]₂(Py)₂ (M=Ni 2, Co 3), have been prepared by the treatment of 4-Hcba with the respective metal nitrate M(NO₃)₂ (M=Cu, Ni, Co) in the presence of pyridine (Py). Single-crystal X-ray diffraction analyses (3 is isostructural to 2) show that the obtained complexes are of isolated mononuclear and the metal atoms have distorted octahedral coordination environment. Two different types of intramolecular hydrogen bonds exist: asymmetrical O–HO for 1 and symmetrical OHO for 2 and 3. The crystal packing between the molecular complexes is controlled mainly by T-shaped C–Hπ interactions between pyridine and phenyl rings. Preliminary discussions on IR, UV–VIS and fluorescent spectra have also been carried out.     

Synthesis of novel platinum-silver and platinum-copper complexes with bridging alkynyl ligands

The study of the reactivity of [Pt₂M₄(CCR)₈] (M=Ag or cu; R=Ph or ^tBu) towards different neutral and anionic ligands is reported. This study reveals that reactions of the phenylacetylide derivatives [Pt₂M₄(CCPh)₈] with anionic, X⁻ (X=Cl or Br) or neutral donors (CN^tBu or py) in a molar ratio 1:4 (m/donor ratio 1:1) yield the trinuclear anionic (NBu₄)₂[{Pt(CCPh)₄ (MX)₂] (M=Ag or Cu, X =Cl or Br) or neutral [{Pt(CCPh0₄=sAGL)₂] (L=CN^tBu or py) complexes, respectively. The crystal structure of (NBu₄)₂[{Pt(CCPh)₄}(CuBr)₂](4) shows that the anion is formed by a dianionic Pt(CCPh)₄ fragment and two neutral CuBr units joined through bridging alkynyl ligands. All the alkynyl groups are σ bonded to Pt and η²-coordinated to a Cu atom which have an approximately trigonal-planar geometry. By contrast, similar reactions with [Pt₂M₄(CC^tBu)₈] (molar ratio M/donor 1:1) afford hexanuclear dianionic (NBu₄)₂[Pt₂M₄(CC^tBu)₈X₂] or neutral [Pt₂Ag₄(CC^tBu0₈Py₂]. Only by treatment with a large exces of Br ⁻ (molar ratio M/Br⁻ 1:2) are the trinuclear complexes (NBu₄)₂[{Pt(CC^tBu₄ (MBr)₂] (M=Ag, Cu) obtained. Attempted preparations of analogous complexes with phosphines (L′=PPh₃ or PEt₃) by reactions of [Pt₂M₄(CCR₈] with L′ leads to displacement of alkynyl ligands from platinum and formation of neutral mononuclear complexes [trans-Pt(CCR)₂L′₂].     

Heterobimetallic Mo---Sn complexes. Reactions of [Mo(CO)3(CH3CN)2(Cl)(SnRCl2)] (R = Me, Ph) with 4(4-XC6H4)3 (X = Cl, F, H, Me, MeO)

Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO)₃(CH₃CN)₂(Cl)(SnRCl₂)] (R = Ph, Me) with P(4-XC₆H₄)₃ (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO)₂(CH₃COCH₃)₂(PPh₃)(Cl)(SnRCl₂)]·nCH₃COCH₃ (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO)₃{P(4-XC₆H₄)₃}(μ-Cl)(SnRCl₂)]₂ (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO)₃(CH₃CN) {P(4-XC₆H₄)₃}(Cl)(SnRCl₂)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes.     

Infrared and Raman study of some isonicotinic acid metal(II) halide and tetracyanonickelate complexes

In this study the M(IN)(2)Ni(CN)(4) [where M: Co, Ni, and Cd, and IN: isonicotinic acid, abbreviated to M-Ni-IN] tetracyanonickelate and some metal halide complexes with the following stoichiometries: M(IN)(6)X(2) (M: Co; X: Cl and Br, and M: Ni; X: Cl, Br and I) and Hg(IN)X(2) (X: Cl, Br, and I) were synthesized for the first time. Certain chemical formulas were determined using elemental analysis results. The FT-IR and Raman spectra of the metal halide complexes were reported in the 4000-0 cm(-1) region. The FT-IR spectra of tetracyanonickelate complexes were also reported in the 4000-400 cm(-1) region. Vibrational assignments were given for all the observed bands. For a given series of isomorphous complexes, the sum of the difference between the values of the vibrational modes of the free isonicotinic acid and coordinated ligand was found to increase in the order of the second ionization potentials of metals. The frequency shifts were also found to be depending on the halogen. The proposed structure of tetracyanonickelate complexes consists of polymeric layers of /M-Ni(CN)(4)/(infinity) with the isonicotinic acid molecules bound directly to the metal atom.     

Übergangsmetall-carbin-komplexe : LXXXIII. Neue anionische mer-dihalogeno-tricarbonyl-dialkylamino-carbin-komplexe des wolframs

The reaction of trans-X(CO)₄WCNR₂ (X = Br, R = ^c hex (cyclohexyl); X = Cl, R = ^c hex, ⁱpr (isopropyl) with M⁺X⁻ (M⁺ = NEt₄⁺, X⁻ = Br⁻; M⁺ = PPN⁺, X⁻ = Cl⁻) leads under substitution of one CO ligand to new anionic dihalo(tricarbonyl)carbyne-tungsten complexes of the type M⁺ mer-[(X)₂(CO)₃WCNR₂]⁻ (M⁺ = NEt₄⁺, X = Br, R = ^c hex; M⁺ = PPN⁺, X = Cl, R = ^c hex, ⁱ pr), whose composition and structure were determined by elemental analysis as well as by IR, ¹H and ¹³C NMR spectroscopy. In the anionic carbyne complexes the entered halogen ligand, coordinated in a cis position relative to the carbyne ligand on the metal, can be easily substituted by neutral nucleophiles, as the reaction of PPN⁺ mer-[(Cl)₂(CO)₃WCN^chex₂]⁻ with PPh₃ demonstrates yielding the neutral carbyne complex mer-[Cl(CO)₃(PPh₃)WCN^chex₂].     

Copper(I) and mercury(II) halide complexes of 1,2-bis(diphenylthioylphosphino)hydrazine

The reaction of 1,2-bis(diphenylthioylphosphino)hydrazine (L) with copper(I) and mercury(II) halides affords the complexes, [{CuLX}₂] (X = I, Br or Cl), [HgLX₂] (X = Cl or Br) and the tetrametallic complex, [{L(HgI₂)₂}₂]. Single crystal X-ray structures have been performed on the uncoordinated ligand, L, as well as the complexes [{CuLX}₂] (X = I, Br and Cl), [HgLBr₂] and [{L(HgI₂)₂}₂. The molecules of L exist as dimers as a result of pairs of N–HS hydrogen bonds. The copper(I) complexes are centrosymmetric dimetallic species, the two copper atoms being bridged by L and the X atoms. In all cases the coordination sphere around the Cu atoms is approximately trigonal pyramidal with an ‘S₂X₂’ donor set. The complex, [HgLBr₂], is a distorted tetrahedral monomer with an ‘S₂Br₂’ donor set and L acting as a bidentate thus forming a seven-membered chelate ring. The tetramercury iodo complex, [{L(HgI₂)₂}₂], contains two ‘L(HgI₂)₂’ units linked centrosymmetrically via an I atom from each moiety. The geometry around the Hg atoms is distorted tetrahedral. The influence of hydrogen bonding between the hydrazine backbone hydrogens of L and the coordinated halide ions in for the structures of the metal complexes is discussed.     

The reactivity of cationic [trioxo-(1,4,7-triazacyclononane) rhenium(VII)] and oxorhenium(V) complexes containing triazamacrocycles

The reduction of colourless [LRe^VIIO₃]Br in an acetone-water mixture (6: 1) with zinc amalgam affords green, air-sensitive [LRe^VO₂Br] which forms a violet complex [LReO(μ-O)₂ReOBr₂]in aqueous solution (L = 1,4,7-triazacyclononane; C₆H₁₅N₃). From a similar reduction of [LReO₃]ReO₄ the violet neutral complex [LReO(μ-O)₂ReO(ReO₄)₂] was obtained. [LReO₃]⁺ is deprotonated in alkaline solution (pK_a = 10.3 + 0.2, 25°C) and [(C₆H₁₄N₃)ReO₃] was isolated as a yellow solid. The latter amido rhenium(VII) compound reacted in dimethylformamide with R---X (R = CH₃, benzyl; X = Cl), affording at the cyclic amine, N,N′,N″-trisalkylated complexes of the type [L′ReO₃]X. The monomeric rhenium(V) complexes [LReOX₂]X (X = Cl, Br, I) were obtained from the reaction of [n-Butyl₄N]ReOX₄ and L in acetonitrile. IR, UV-vis, ¹⁷O NMR spectra of these compounds are reported.     

Vibrational spectra, structure and hydrogen bonding of 5-tert-butylpyrazole and its zinc complexes

New zinc complexes [L₂ZnX₂] with X=Cl (I), Br (II), I (III) and NO₃ (IV), [L₃Zn(OClO₃)]ClO₄ (V) and [L₄Zn](ClO₄)₂ (VI) with 5-tert-butylpyrazole as ligand L were synthesized and characterized by infrared-, Raman-, mass- and NMR-spectroscopy. The assignment of the vibrational frequencies for the complexes in the range of 4000–80 cm⁻¹ is proposed. Analysis of the IR spectra in the range of ν_NH frequencies shows that 5-tert-butylpyrazole forms cyclic associates in the solid using intermolecular NHN hydrogen bonds. This was proven by a crystal structure determination, which showed that L exists as tetramers in the solid state. In solution there is an equilibrium between tetramers and monomers and, probably, dimers or trimers. In the complexes, the NH-groups of L form intramolecular H-bonds with the X-group. The intramolecular H-bond in VI has interionic character and partially dissociates in solution at high dilution. Ligand vibrations that are sensitive to the coordination and the dependence of their frequencies on the anionic group X has been revealed.     

Indazole complexes of diorganotin(IV) dihalides. The crystal structures of dichloro and dibromodimethylbis(indazole) tin(IV)

Reaction of indazole (HInd) with diorganotin(IV) dihalides yielded compounds of the type [SnR₂X₂(HInd)₂] (R = Me, Et, Bu and Ph; X = Cl, Br). The structures of the dihalodimethylbis(indazole)tin(IV) complexes were determined by X-ray crystallography. These are trans-octahedral centrosymmetric compounds with the following bond lengths (Å) around the tin atom: Sn-Cl 2.590(2), Sn-N 2.377(6), Sn-C 2.12(1) in the chloride; and Sn-Br 2.733(1), Sn-N 2.370(5) and Sn-C 2.12(1) in the bromide. Mössbauer and vibrational spectra suggest similar trans stereochemistry for the other complexes prepared. The behaviour of these compounds in solution was studied by conductimetry and NMR techniques.     

吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、 表征及催化合成液体聚丁二烯

合成了一系列吡啶双亚胺酰氯三齿Ni(Ⅱ) 配合物(1a~1c, 2a~2c), 通过傅里叶变换红外光谱和元素分析对配合物进行表征, 测定了配合物1a~1c的晶体结构. 3个化合物同属于单斜晶系, 且都具有以Ni原子为中心的近似于C_s对称的扭曲三角双锥构型. 该系列配合物通过倍半乙基氯化铝(EASC)活化, 在20 ℃下对丁二烯聚合表现出良好的催化活性, 得到分子量为4700~5200、 cis-1,4含量为74.8%~77.2%(摩尔分数)的液体聚丁二烯. 通过改变配体的结构和聚合条件, 可在一定范围内调控聚丁二烯的结构和分子量.     

Coordination chemistry of chelating nitrogen ligands with tungsten carbonyl nitriles

The reactions of a series of Schiff base ligands (1–4) prepared by condensation of pyridine-2-carboxaldehyde and 2-X-anilines (X = F, Cl, Br, OMe) with W(CO)₃(RCN)₃ results in the formation of deeply coloured complexes W(CO)₃(1–4)(NCR) which readily react with carbon monoxide to afford W(CO)₄(1–4). The ligand 5, prepared from pyridine-2-carboxaldehyde and N,N-dimethylethylenediamine, coordinates to W(CO)₃ through the conjugated pyridine—imine chelate to afford complexes with a pendant dimethylamino group which reacts with electrophiles. Of the ligands studied, only the bis-amine, pyridine ligand 8, coordinates to W(CO)₃ in a tridentate manner. These reactions provide insight into the geometric and electronic factors which influence coordination of nitrogen containing ligands at a fac-tricarbonyl metal centre.     

Co-ordination compounds of diacetyldihydrazone and diacetylbis(monomethylhydrazone)

Summary Diacetyldihydrazone (DADH) forms only six-coordinate complexes with iron(II), cobalt(II), nickel(II) and zinc(II). In M(DADH)₂X₂ (M=Fe, X=Br or I; M=Co, X=I; M=Ni, X=Cl, Br or NCS) the ligand is chelating in the [M(DADH)₃]²⁺ cations, while in M(DADH)₂X₂ (M=Co, X=Cl or Br; M=Ni, X=Cl or Br) the ligand is probably bridging and bidentate. Diacetylbismonomethylhydrazone (DAMH), by contrast, forms predominantly tetrahedral complexes M(DAMH)X₂ (M=Fe or Co, X=Cl or Br; M=Ni, X=Br; M=Co, X=NCS; M=Zn, X=Cl, Br or NCS) and some octahedral complexes M(DAMH)₂X₂ (M=Co, X=NCS; M=Ni, X=Br). The i.r. spectra, electronic spectra and magnetic moments of the complexes are discussed.     

Transition metal sulfur dioxide hexafluoroarsenates and hexafluoroantimonates

The preparation and characterization by X-ray crystallography of transition metal sulfur dioxide hexafluoroarsenates of the general formula [M(SO₂)_x](AsF₆)₂ 1 (1a: M=Mn, x=2; 1c: M=Co, x=4; 1e: M=Cu, x=4) and the hexafluoroantimonate [Co(SO₂)₂](SbF₆)₂ 3 is reported. The structural features of the compounds mentioned are compared with those of [Fe(SO₂)₄](AsF₆)₂ (1b) and [Ni(SO₂)₆](AsF₆)₂ (1d), reported previously. The structural diversity of transition metal sulfur dioxide complexes is discussed.     

Synthesis and characterisation of nickel(II) complexes with tripodal ligand tris[4-(3-(5-methylpyrazolyl)-3-aza-3-butenyl] amine (MPz3tren): X-ray crystal structure of [Ni(MPz3tren)](BF4)2·0.5H2O

Nickel(II) complexes of the tripodal ligand (MPz₃tren) of the general formula [Ni(MPz₃tren)]X₂·nH₂O (X=Cl, Br, NO₃, ClO₄ and BF₄; n=0 for Cl and Br; n=0.5 for NO₃, ClO₄ and BF₄) have been prepared by template methodology and characterised by elemental analyses, magnetic susceptibility and conductivity measurements at RT, IR and electronic spectra. The molar conductivities measured in MeOH for all the complexes show them to be 1:2 electrolytes. The hexadentate character of the ligand in all the complexes is inferred from IR spectral studies. The electronic spectra in solid state and in MeOH solution suggest octahedral geometry for all the complexes. The structure of [Ni(MPz₃tren)](BF₄)₂·0.5H₂O has been determined by single-crystal X-ray diffraction studies (monoclinic, c2/c). Nickel(II) is in a trigonal antiprismatic N₆ donor environment and the crystal structure is stabilised by a network of strong H-bonding.     

Metal Complexes of Aniline: Infrared and Raman Spectra

Abstract

The literature for the years 1965–1987 has been searched for all significant papers which refer to the vibrational spectra of metal complexes of aniline and substituted anilines. These papers have been reviewed with particular reference to isotopic labelling and metal ion substitution studies as assignment techniques and to the structural and bonding information which can be derived from the spectra. Compounds of the following classes are included: [M(an)₂X₂] (M = Mn, Co, Ni, Cu, Zn, Cd, Hg; an = aniline, X - Cl, Br, I, NCS); cis- and trans-[Pt(an)₂X₂] (X = Cl, Br, I, NO₂); [M(R-an)₂X₂] (M = Mn, Co, Ni, Cu, Zn; R-an = o-, m- and p-toluidine and other substituted anilines; X = Cl, Br, I); aniline adducts of metal β-ketoenolates; the complexes trans-[PtL(R-an)X₂] (L = CH₂?CH₂ or CO, R-an = aniline or a substtuted aniline, X = Cl, Br); and other miscellaneous systems comprising aniline as a ligand.     

Cobalt and nickel complexes bearing 2,6-bis (imino) phenoxy ligands: syntheses, structures and oligomerization studies

A series of new cobalt and nickel complexes LMX₂ (M=Co, X=Cl; M=Ni, X=Br) bearing 2, 6-bis(imino)phenoxy ligands were synthesized. The solid-state structures of 1 and 4 have been determined by single-crystal X-ray diffraction study. Treatment of the complexes LMX₂ with methylaluminoxane (MAO) leads to active catalysts for oligomerization of ethylene with catalytic activities in the range of 1.2×10⁵–2.1×10⁵ g mol⁻¹ h⁻¹ atm⁻¹ for Ni complexes, and 10³ g mol⁻¹ h⁻¹ atm⁻¹ for Co complexes. The oligomers were olefins from C₄ to C₁₆.     

Organometallic complexes for nonlinear optics: Part 32: Synthesis, optical spectroscopy and theoretical studies of some osmium alkynyl complexes

The complexes trans-[Os(CCPh)Cl(dppe)₂] (1), trans-[Os(4-CCC₆H₄CCPh)Cl(dppe)₂] (2), and 1,3,5-{trans-[OsCl(dppe)₂(4-CCC₆H₄CC)]}₃C₆H₃ (3) have been prepared. Cyclic voltammetric studies reveal a quasi-reversible oxidation process for each complex at 0.36–0.39 V (with respect to the ferrocene/ferrocenium couple at 0.56 V), assigned to the Os^II/III couple. In situ oxidation of 1–3 using an optically transparent thin-layer electrochemical (OTTLE) cell affords the UV–Vis–NIR spectra of the corresponding cationic complexes 1⁺–3⁺; a low-energy band is observed in the near-IR region (11 000–14 000 cm⁻¹) in each case, in contrast to the neutral complexes 1–3 which are optically transparent below 20 000 cm⁻¹. Density functional theory calculations on the model compounds trans-[Os(CCPh)Cl(PH₃)₄] and trans-[Os(4-CCC₆H₄CCPh)Cl(PH₃)₄] have been used to rationalize the observed optical spectra and suggest that the low-energy bands in the spectra of the cationic complexes can be assigned to transitions involving orbitals delocalized over the metal, chloro and alkynyl ligands. These intense bands have potential utility in switching nonlinear optical response, of interest in optical technology.