13463-39-3Relevant articles and documents
Icosahedral Ga-centred nickel carbonyl clusters: Synthesis and characterization of [H3-nNi12 (μ12-Ga)(CO) 22]n- (n = 2, 3) and [Ni14.3(μ12- Ga)(CO)24.3]3- anions
Femoni, Cristina,Iapalucci, Maria Carmela,Longoni, Giuliano,Zacchini, Stefano
, p. 1056 - 1062 (2010)
The reaction of [Ni5(CO)12]2- or [Ni 6(CO)12]2- with GaCl3 in dichloromethane under a nitrogen atmosphere affords a mixture of [Ni 12+x(μ12-Ga)(CO)22+x]3- (x = 0-3) clusters. Short exposure of the above mixture to a carbon monoxide atmosphere leads to the green icosahedral [Ni12(μ12-Ga)(CO) 22]3- trianion, which was isolated and characterized as its [NnBu4]+ salt. In contrast, crystallization of the above mixture in the presence of Ni(CO)4 enabled isolation of a cocrystallized mixture of [Ni14(μ12-Ga)(CO) 24]3- (70%) and [Ni15(μ12-Ga)(CO) 25]3- (30%). As inferable from its structure, the additional three Ni(CO) moieties condense onto interlayer faces of the icosahedron. Protonation of [Ni12(μ12-Ga)-(CO) 22]3- affords the corresponding [HNi12(μ 12-Ga)(CO)22]2- hydride derivative, which was isolated in a pure state and fully characterized. All of the above compounds conform to the cluster-borane analogy, by the inclusion principle, and none exhibits relevant redox behaviour.
Klabunde,Efner
, p. 114 (1974)
Blanchard, A. A.,Rafter, J. R.,Adams, W. B.
, p. 16 - 17 (1934)
Groot, P. de,Coulon, M.,Dransfeld, K.
, p. 204 - 220 (1980)
Ettmayer, P.,Jangg, G.
, (1961)
Blanchard, A. A.
, p. 3 - 39 (1937)
Ostwald, W.
, p. 204 (1914)
A study of Cu/ZnO/Al2O3 methanol catalysts prepared by flame combustion synthesis
Jensen,Johannessen,Wedel,Livbjerg
, p. 67 - 77 (2003)
The flame combustion synthesis of Cu/ZnO/Al2O3 catalysts for the synthesis of methanol from CO, CO2, and H2 was studied. A low peak temperature and quench cooling of the flame tended to increase the dispersion of the phases and the specific surface area of the particles. The specific surface area varied from ≤ 100 sq m/g for samples without aluminum to several hundred square m per gram for the respective compositions of pure Al2O3 and ZnAl2O4. The samples prepared and tested with copper as one of the components showed potential for use as methanol catalysts. The contribution of ZnAl2O4 to an increased surface area and thermal stability was the explanation of the beneficial role of alumina in the methanol synthesis catalyst. Although Cu/Al2O3 showed methanol synthesis activity, the Cu-based turnover frequency was inferior to that of the ZnO-containing catalysts. Methane, which is the only detectable by-product of the reaction, was produced in minute amounts unless the catalyst was contaminated by nickel.
Steric and electronic properties of N-heterocyclic carbenes (NHC): A detailed study on their interaction with Ni(CO)4
Dorta, Reto,Scott, Natalie M.,Costabile, Chiara,Cavallo, Luigi,Hoff, Carl D.,Nolan, Steven P.
, p. 2485 - 2495 (2005)
N-heterocyclic carbene ligands IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5) react with Ni(CO)4 to give the saturated tricarbonyl complexes Ni(CO)3(IMeS) (8), Ni(CO)3(SIMeS) (9), Ni(CO)3(IPr) (10), Ni(CO)3(SIPr) (11), and Ni(CO) 3(ICy) (12), respectively. The electronic properties of these complexes have been compared to their phosphine analogues of general formula Ni(CO)3(PR3) by recording their vco stretching frequencies. While all of these NHCs are better donors than tertiary phosphines, the differences in donor properties between ligands 1-5 are surprisingly small. Novel, unsaturated Ni(CO)2(IAd) (13) and Ni(CO)2(I tBu) (14) compounds are obtained from the reaction of Ni(CO) 4 with IAd (6) and ItBu (7). Complexes 13 and 14 are highly active toward substitution of the NHC as well as the carbonyl ligands. This has allowed the determination of Ni-C(NHC) bond dissociation energies and the synthesis of various unsaturated Ni(0) and Ni(II) complexes. Computational studies on compounds 8-14 are in line with the experimental findings and show that IAd (6) and ItBu (7) are more bulky than IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5). Furthermore, a method based on % Vbur values has been developed for the direct comparison of steric requirements of NHCs and tertiary phosphines. Complexes 8-14, as well as NiCl(C 3H5)(ItBu) (16) and NiBr(C3H 5)(ItBu) (17), have been characterized by X-ray crystallography.
Hieber, W.,Brueck, R.
, p. 312 - 313 (1949)
Condensation of nickel-carbonyl clusters with soft lewis acids: Synthesis and characterisation of the {Cd2Cl3[Ni6(CO) 12]2}3- dimer
Femoni, Cristina,Iapalucci, Maria Carmela,Longoni, Giuliano,Ranuzzi, Fabrizio,Zacchini, Stefano,Fedi, Serena,Zanello, Piero
, p. 4064 - 4070 (2007)
Reaction of [Ni6(CO)12]2- in thf with 2 equiv. of the soft Lewis acid CdCl2·2.5H2O gives the new dimeric species {Cd2Cl3[Ni6(CO) 12]2}3-/su
Reactions of laser-ablated Ni, Pd, and Pt atoms with carbon monoxide: Matrix infrared spectra and density functional calculations on M(CO)n (n = 1-4), M(CO)n- (n = 1-3), and M(CO)n+ (n = 1-2), (M = Ni, Pd, Pt)
Andrews,Liang,Zhou
, p. 3905 - 3914 (2000)
There has always been extra focus on the bonding characteristics of monocarbonyls since they are deemed as the models of the CO binding to the metal surface. Laser-ablated Ni, Pd, and Pt atoms were reacted with CO molecules during condensation in a neon matrix at 4 K. Annealing, photolysis, and isotopic substitution experiments identified metal carbonyl anions [M(CO)n- (n = 1-3)] and cations [Ni(CO)n+ (n = 1-4); Pd(CO)n+ (n = 1,2); Pt(CO)n+ (n = 1-3)], and neutrals [M(CO)n (n = 1-4)]. Doping with the CCl4 electron trap increased cation and decreased anion absorptions and supported the identification of the ionic species. The density functional theory (DFT) calculations showed that experimental results agreed excellently with frequencies and isotopic frequency ratios, confirming the vibrational assignments and the identification of these metal carbonyl complexes. All the monocarbonyls were linear, except PdCO- and PtCO-, which were computed to be bent by both DFT/B3LYP and BP86 functionals. Natural bonding orbital analysis on the monocarbonyls, conducted to describe the bonding of CO to transition metals, showed that: C-O bond orders were cations > neutrals > anions, indicating that C-O stretching frequencies have the same order as seen for other transition metals; and the various configurations of metal atoms in anions, cations, or neutrals could be employed to explain the different geometries.
Preparation and identification of intermediate carbonyls of nickel and tantalum by matrix isolation
DeKock
, p. 1205 - 1211 (1971)
All four carbonyls of nickel, Ni(CO)1-4, and possibly six carbonyls of tantalum, Ta(CO)1-6, have been identified via infrared spectra in argon matrices at 4.2°K. The carbonyls are prepared by the vaporization of the metal atoms and condensation into a CO-argon mixture. C18O was also used in the identification. Careful warming of the matrix results in the growth and disappearance of νco bands in the 2000-cm-1 region. In the nickel experiments these bands appear at 2052, 2017, 1967, and 1996 cm-1 and are assigned to Ni(CO)4, Ni(CO)3, Ni(CO)2, and NiCO, respectively. Specific assignments for tantalum carbonyls are more difficult, but five or six molecules are definitely formed during the diffusion experiments. For the tantalum carbonyls also, the general trend is that the stretching frequencies increase with increasing coordination number, a fact which is predicted on the basis of simple bonding theory. In the electronic spectra broad absorptions at 3000 and 2725 A? are attributed to Ni(CO)4 and Ta(CO)6, respectively.
Mixed Co-Ni Carbide Clusters. Part 1. Synthesis and Structural Characterization of the 3- Trianion
Ceriotti, Alessandro,Pergola, Roberto Della,Longoni, Giuliano,Manassero, Mario,Sansoni, Mirella
, p. 1181 - 1186 (1984)
Reaction of with 2- results in a complicated mixture of mixed Co-Ni carbide carbonyl clusters, among which the 3- trianion has been isolated in a pure crystalline state and fully characterized by X-ray crystallography.The metal framework of this compound is unprecedented in cluster geometries and may be described as a square antiprism of metal atoms tetra-capped on two alternate pairs of adjacent triangular faces.Despite the presence of a caged carbon atom in the square-antiprismatic cavity, the compound is readily degraded by carbon monoxide (25 deg C, 1 atm) mainly to a mixture of - and .Corresponding degradation of the cluster under a mixture of carbon monoxide and hydrogen yields, in addition, trace amounts of organics, mainly C1 and C2 hydrocarbons, probably derived from the carbide atom.
Determinations des temperatures et des pressions par spectrometric Raman au cours de la CVT du nickel
Monteil, Y.,Raffin, P.,Bouix, J.
, p. 429 - 436 (1988)
Nickel CVT, based on the following chemical equilibrium: Ni(s) + 4CO(g) Ni(CO)4(g), has been studied by Raman spectroscopy.The temperature of the gaseous mixture can be calculated from the experimental intensities of CO rotational Raman-Stokes lines.The simulation of CO spectrum has been made from the theoretical intensities of lines convoluted with functions taking account of the incident band shape (Gaussian function) and slit geometry (apparatus function).Simulated and experimental spectra are in a good agreement and the calculated temperature is found with a precision of one Celsius degree compared with the temperature at 1/10 deg C precisely.From the Ni(CO)4 vibration VS(Al) at 370.6 cm-1 available both in Stokes and anti-Stokes fields, we have another method of temperature calculation (SAS method).At a known temperature, the same vibration can be used to compute the partial pressure of Ni(CO)4.Results obtained are compared with those directly measured with a tensimeter.The temperature and the pressure respectively determined from the CO rotation lines and the Ni-C symmetric streching vibration at 370.6 cm- permit us to follow the nickel CVT in a transparent furnace (SnO2 technology).
tmeda-Nickel-Komplexe III. (N,N,N',N'-Tetramethylethylendiamin)-(dimethyl)nickel(II)
Kaschube, Wilfried,Poerschke, Klaus R.,Wilke, Guenther
, p. 525 - 532 (1988)
(tmeda)Ni(acac)2 reacts with the main group metal compounds (tmeda)Mg(CH3)2, (tmeda)2, and (C2H5O)Al(CH3)2 at 0 deg C to give (tmeda)Ni(CH3)2 (1), which can be isolated as fine yellow crystals in 50-80 percent yield.Complex 1, which is the simplest dialkyl nickel(II) compound with a hard donor ligand, is suprisingly stable and decomposes only at 79 deg C. 1 is converted by bipy to (bipy)Ni(CH3)2 and by Me2PC2H4PMe2 to (Me2PC2H4PMe2)Ni(CH3)2.Upon reaction of 1 with strong ?-acceptor molecules (acrylic acid methylester, methyl vinyl ketone, acrylonitrile, tetracyanoethene, tetrafluoroethene, maleic anyhdride) reductive elimination of the methyl groups takes place to give the complexes (tmeda)Ni(?-ligand)n (n=1,2) and ethane.
An in situ CIR-FTIR investigation of process effects in the nickel catalyzed carbonylation of methanol
Moser, William R.,Marshik-Guerts, Barbara J.,Okrasinski, Stanley J.
, p. 57 - 69 (1999)
The carbonylation of methanol to form methyl acetate and acetic acid was investigated using phosphine modified nickel iodide as the metal catalyst precursor. The course of the reaction was monitored using a high pressure, high temperature in situ Cylindrical Internal Reflectance FTIR reactor (CIR- REACTOR) to acquire data under autogenous conditions. The capabilities of the reactor permit reaction monitoring at temperatures of 190°C and pressures of 13.6 kPa (1500 psig). In this study the reaction kinetics and in situ observations were made at temperatures between ambient and 160°C with an operating pressure of 8.16 kPa (900 psig) for most reactions. This study used methyl acetate as a solvent, and both methyl acetate and acetic acid were products of the catalytic reaction. Conditions were optimized at 160°C using organo-phosphine modified NiI2 as the catalyst precursor. Under the applied reaction conditions, no anionic carbonyl species such as Ni(CO)(x)I(y)/(-y) were detected at high carbonylation rates, in contrast to the anionic carbonyls reported in the rhodium catalyzed acetic acid process. In the rapid kinetic regime, only trace amounts of Ni(CO)4 were formed in the reactor at steady state. The experimental results suggest a new mechanism involving Ni(PPh3)2 as one of the active metal complex intermediates reacting in a slow step with methyl iodide. The in situ reaction monitoring experiments readily enabled the determination of the concentrations of organonickel species as well as the concentration of carbonylation products under fast reaction conditions.
Barnett, K. W.
, p. 477 - 485 (1970)
Pathways for Reduction on Nickelocene under CO
Payne, John D.,Murr, Nabil El
, p. 1137 - 1138 (1984)
Cyclic voltammetry under CO has been used to show that the short-lived nickelocene anion splits into NiCp and Cp- (Cp = C5H5) fragments; trapping of the NiCp moiety with CO leads to -, which under high CO pressure loses a further Cp- to give Ni(CO)4.
Bimetallic nickel-cobalt hexacarbido carbonyl clusters [H 6-nNi22Co6C6(CO)36] n- (n = 3-6) possessing polyhydride nature and their base-induced degradation to the monoacetylide [Ni9CoC2(CO) 16- x]3- (x = 0, 1)
Ciabatti, Iacopo,Femoni, Cristina,Iapalucci, Maria Carmela,Longoni, Giuliano,Zacchini, Stefano
, p. 4593 - 4600 (2012)
The reaction of [Ni10C2(CO)16] 2- with Co3(μ3-CCl)(CO)9 results in the new bimetallic Ni-Co hexacarbido carbonyl clusters [H 6-nNi22Co6C6(CO)36] n- (n = 3-6), which possess polyhydride nature and can be interconverted by means of acid-base reactions. The tetra-anion [H 2Ni22Co6C6(CO)36] 4- and the hexa-anion [Ni22Co6C 6(CO)36]6- have been isolated in a crystalline state and structurally characterized via X-ray crystallography. The six carbide atoms are lodged into Ni7CoC square antiprismatic cages. Addition of strong bases to [Ni22Co6C6(CO) 36]6- affords mixtures of the monoacetylides [Ni 9CoC2(CO)16]3- and [Ni 9CoC2(CO)15]3-, which have been cocrystallized as [NEt4]3[Ni9CoC 2(CO)16-x] (x = 0.58-0.84) salts, displaying tightly bonded interstitial C2 units.
THE REACTIONS OF IRON-CARBONYL AND ALKYNE-CARBONYL COMPLEXES WITH NICKELOCENE, 2 AND (η-C5H5)2Ni2(RC2R'). CRYSTAL STRUCTURES OF TWO HETEROMETALLIC TETRANUCLEAR CLUSTERS
Sappa, Enrico,Tiripicchio, Antonio,Camellini, Marisa Tiripicchio
, p. 243 - 264 (1980)
The reaction of nickelocene, 2 and its alkyne-substituted derivatives with Fe(CO)5, Fe3(CO)12 and alkyne-cluster derivatives of iron are reported and discussed.A considerable number of new heterometallic complexes has been obtained: the structures of the two tetranuclear complexes (η-C5H5)2Ni2Fe2(CO)7 (I) and (η-C5H5)2Ni2Fe2(CO)6(C2Et2) (IIa) have been determined by X-ray diffraction methods.Crystals of I are triclinic, a 8.028(8), b 14.561(12), c 7.961(8) Angstroem; α 94.58(7), β 97.26(11), γ 92.23(9)o; space group P.Crystals of IIa are triclinic, a 10.124(10), b 14.676(12), c 8.396(8) Angstroem; α 95.80(8), β 111.20(10), γ 72.89(9)o, space group P.Both structures have been solved from diffractometer data by Patterson and Fourier methods and refined by full-matrix least-squares to R=0.039 for I and 0.045 for IIa.The structure of I is characterized by a tetrahedral metal atom core, bound to two cyclopentadienyl ligands (through the Ni atoms) and to six terminal CO's (through the Fe atoms).The seventh carbonyl is triply bridging between two Fe and one Ni atoms in an asymmetric way.The structure of IIa consists of a tetrahedrally distorted square arrangement of two Fe and two Ni atoms.The alkyne is ?-bonded to the Ni atoms and ?-bonded to the Fe atoms.The formation of heterometallic complexes in the above reactions is not selective, although the stability of the cluster reactants, and the nature of the bonding and the substituents in the alkynes can influence the nature and the yields of the products.
Carbon–Fluorine Reductive Elimination from Nickel(III) Complexes
Lee, Heejun,B?rgel, Jonas,Ritter, Tobias
supporting information, p. 6966 - 6969 (2017/06/06)
We report a C?F reductive elimination from a characterized first-row aryl metal fluoride complex. Reductive elimination from the presented nickel(III) complexes is faster than C?F bond formation from any other characterized aryl metal fluoride complex.
