Nickel Carbonyl Research Articles

Efficient Synthesis of Polycyclic γ-Lactams by Catalytic Carbonylation of Ene-Imines via Nickelacycle Intermediates.

The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)3 L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams.

Difunctional nickel/microfiber attapulgite modified with an acidic ionic liquid for catalytic hydroconversion of lignite-related model compounds

Modified microfiber attapulgite (MFA)-supported nickel was prepared by thermally decomposing nickel tetracarbonyl on MFA modified with an acidic ionic liquid (AIL, 1-sulfobutyl-3-methylimidazolium trifluoromethanesulfonate). It was characterized with multiple instruments and used for catalyzing hydroconversion of lignite-related model compounds (LRMCs) oxydibenzene, benzyloxybenzene, and oxybis(methylene)dibenzene. The results indicate that Ni15%/MFA@AIL effectively catalyzes hydroconversion of the LRMCs to afford cyclanes by inducing the formation of H+, H−, and biatomic active hydrogen.

Synthesis and Reactivity of Cyclic (Alkyl)(Amino)Carbene Stabilized Nickel Carbonyl Complexes

Cyclic (alkyl)(amino)carbenes cAACcy (1b) and cAACmenthyl (1c) react with [Ni(CO)4] to give the 18 VE complexes [Ni(CO)3(cAACcy)] (2b) and [Ni(CO)3(cAACmenthyl)] (2c). With these in hand, the donor-strength and the steric profile of the respective cAAC ligands were evaluated. CAACcy and cAACmenthyl possess similar overall-donating properties (Tolman electronic parameter (TEP) = 2046 (1b) and 2042 (1c)) as common NHCs, though they are also known to be better π-acceptors. 3,3-Diamino-2-aryloxyacrylimidamide 3b, arising from the reaction of cAACcy (1b) with released CO molecules, was obtained as side-product of CO substitution reactions at nickel carbonyls. In contrast to cAACmenthyl (%Vbur = 42), the sterically less encumbered cAACcy (%Vbur = 38) undergoes a subsequent CO substitution at [Ni(CO)3(cAACCy)] (2b) to afford the 16 VE complex [Ni(CO)(cAACcy)2] (4b). Treatment of both [Ni(CO)3(cAACmethyl)] (2a) and [Ni(CO)(cAACmethyl)2] (4a) with allyl bromides led to the formation of cAAC-stabilized allyl nickel...

An acidic ionic liquid modified microfiber attapulgite-supported nickel for catalytic hydroconversion of α,ω-diarylalkanes

An acidic ionic liquid modified microfiber attapulgite (MFA)-supported nickel was prepared by thermally decomposing nickel tetracarbonyl onto MFA modified with an acidic ion liquid (AIL, 1-sulfobutyl-3-methylimidazolium trifluoromethanesulfonate). It was characterized with multiple instruments and used for catalyzing hydroconversion of coal-related model compounds (CRMCs) di(1-naphthyl)methane, diphenylmethane, bibenzyl, and 1,3-diphenylpropane. The results indicate that Ni/MFA@AIL effectively catalyzes hydroconversion of the CRMCs to afford cyclanes and alkylcyclanes by inducing the formation of H+, H−, and biatomic active hydrogen species.

Laws governing the combustion of the Ni + Al system under a low ambient gas pressure

The ambient pressure dependences of the combustion rate and combustion-induced elongation for an initial Ni + Al mixture and Ni + Al mixtures subjected to vacuum heat treatment (VHT), mechanical activation, and additional activation in water (dispersion) have been studied. Most of the studies have been conducted for mixtures based on PNK-brand nickel (carbonyl); a separate set of experiments has been conducted for PNE-brand nickel (electrolytic). These powder brands contain different amounts of impurity gases and have different particle sizes. It has been shown that VHT, the ambient gas pressure, and the type of the used nickel have a substantial effect on the combustion rate of these mixtures. For the mixtures based on PNK nickel, the increase in the combustion rate after VHT is more significant than that after mechanical activation despite a more thorough mixing of the precursors and changes in the mixture microstructure. The qualitative change in the behavior of the dependence of the combustion rate of the dispersed mixtures on the external gas pressure has been interpreted in terms of a convective–conductive combustion model. The studies have made it possible to prove the previously made conclusion about the gasless combustion of Ni + Al mixtures (PNK nickel) under high ambient gas pressures.

High-resolution CT features of pulmonary injury induced by acute nickel carbonyl poisoning

目的 回顾性分析急性羰基镍中毒性肺损伤的高分辨率（HR）CT表现。 方法 收集2012年12月接受住院治疗的4例急性羰基镍中毒性肺损伤患者，其中重度中毒3例、中度中毒1例。均为男性；年龄30~41岁，平均36.75岁。中毒后第4天均行首次胸部HRCT平扫4例，其中在中毒后第10天行胸部HRCT复查3例，第15天及第16天再次HRCT复查各1例。 结果 4例患者在中毒后第2天均出现胸闷和呼吸困难，第4天出现轻度口唇紫绀；其中3例重度中毒病例的氧合指数为130~191 mmHg，中度中毒病例的氧合指数为212mmHg。在中毒后第4天，3例重度中毒病例在HRCT上主要表现为双肺弥漫性分布的磨玻璃影伴有实变，实变位于肺的后部；中毒后第10天，实变完全吸收3例，磨玻璃影明显吸收2例及无吸收1例；第15天及第16天HRCT复查各1例，磨玻璃影均有不同程度的吸收。1例中度中毒病例在中毒后第4天呈双肺散在分布的斑片状磨玻璃影。 结论 急性羰基镍中毒性肺损伤的主要HRCT表现是双肺弥漫或散在分布的磨玻璃影伴有或不伴有实变；双肺弥漫分布的磨玻璃影伴有位于肺后部的实变，提示病变进展为急性呼吸窘迫综合征，确诊需结合氧合指数。

Understanding the Oxidation Behavior of Fe/Ni/Cr and Fe/Cr/Ni Core/Alloy Nanoparticles

In this work we describe a method to prepare core/alloy nanoparticles (CA-NPs) based on transition metal alloys with tunable oxidation properties. We investigated the use of chromium and nickel carbonyl based precursors to control shell deposition and thickness at α-Fe cores producing Fe/Cr/Ni and Fe/Ni/Cr CA-NPs. We compared the systems by monitoring resistance to oxidation and found that it is highly dependent on the shell and alloy sequence as well as thickness, with thin Fe/Cr/Ni having the best stainless behavior. The CA-NP growth was monitored by TEM, and composition was assessed by XPS. Oxidation was quantified by both powder XRD and XPS. The results were analyzed in light of alloy miscibility and diffusion, as well as lattice strains and interfacial oxidation rates.

Producing hardfacing composite materials for ecologically safe technologies

The application of hardfacing materials for producing high-strength coatings on components working in abrasive wear conditions is one of the important directions of research into increasing the service life of road construction, agricultural and other types of equipment. However, in producing this equipment, the ecological safety requirements are sometimes ignored and this results in negative effects on the environment and the health of personnel. This article describes the results of scientific and research investigations of the team of authors to develop a cladding powder by the method of chemical gas phase deposition of nickel tetracarbonyl on the surface of aluminium oxide particles and application of the powder for producing wear-resistant coatings. The powder materials are deposited in a closed cycle excluding contact of the personnel with toxic substances and emission of contaminants into the atmosphere, resulting in a safe process. Plasma coatings with the required physical–mechanical properties have been produced. This confirms the efficiency of the approaches used in this case and increases the service life of working sections of machines subjected to abrasive wear.

Detachment of CVD-grown graphene from single crystalline Ni films by a pure gas phase reaction

Despite great previous efforts there is still a high need for a simple, clean, and upscalable method for detaching epitaxial graphene from the metal support on which it was grown. We present a method based on a pure gas phase reaction that is free of solvents and polymer supports and avoids mechanical transfer steps. The graphene was grown on 150nm thick, single crystalline Ni(111) films on Si(111) wafers with YSZ buffer layers. Its quality was monitored by using low energy electron diffraction and scanning tunneling microscopy. The gas phase etching uses a chemical transport reaction, the so-called Mond process, based on the formation of gaseous nickel tetracarbonyl in ~1bar of CO at ~75°C and by adding small amounts of sulfide catalysts. X-ray photoelectron spectroscopy, Raman spectroscopy and scanning electron microscopy were used to characterize the detached graphene. It was found that the method successfully removes the nickel from underneath the graphene layer, so that the graphene lies on the insulating oxide buffer layer. Small residual particles of nickel sulfide and cracks in the obtained graphene layer were identified. The defect concentrations were comparable to graphene samples obtained by wet chemical etching and by the bubbling transfer.

Photoelectron velocity-map imaging and theoretical studies of heteronuclear metal carbonyls MNi(CO)3− (M = Mg, Ca, Al)

The heteronuclear metal carbonyl anions MNi(CO)3(-) (M = Mg, Ca, Al) have been investigated using photoelectron velocity-map imaging spectroscopy. Electron affinities of neutral MNi(CO)3 (M = Mg, Ca, Al) are measured from the photoelectron spectra to be 1.064 ± 0.063, 1.050 ± 0.064, and 1.541 ± 0.040 eV, respectively. The C-O stretching mode in these three clusters is observed and the vibrational frequency is determined to be 2049, 2000, and 2041 cm(-1) for MgNi(CO)3, CaNi(CO)3, and AlNi(CO)3, respectively. Density functional theory calculations are carried out to elucidate the geometric and electronic structures and to aid the experimental assignments. It has been found that three terminal carbonyls are preferentially bonded to the nickel atom in these heterobinuclear nickel carbonyls MNi(CO)3 (-1/0), resulting in the formation of the Ni(CO)3 motif. Ni remains the 18-electron configuration for MgNi(CO)3 and CaNi(CO)3 neutrals, but not for AlNi(CO)3. This is different from the homobinuclear nickel carbonyl Ni-Ni(CO)3 with the involvement of three bridging ligands. Present findings would be helpful for understanding CO adsorption on alloy surfaces.

Catalytic hydroconversion of methanol-soluble portion from Xiaolongtan lignite over difunctional Ni/Z5A

A highly active difunctional supported nickel catalyst Ni/Z5A was prepared by thermally decomposing nickel carbonyl onto zeolite 5A (Z5A). The catalytic hydroconversion (CHC) of methanol-soluble portion (MSP) from the methanolysis of Xiaolongtan lignite was investigated over Ni/Z5A at 200°C. Detailed molecular compositions of MSP and catalytically hydrogenated MSP (CHMSP) were characterized with a Fourier transform infrared spectrometer, gas chromatograph/mass spectrometer (GC/MS), and negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer (ESIFTICRMS). According to analysis with GC/MS, MSP is rich in aromatic ring- and/or heteroatom-containing compounds, while most of the GC/MS-detectable compounds in CHMSP are chain alkanes and cyclanes. The analysis with ESIFTICRMS shows that both the number and yields of oxygen- and/or nitrogen-containing species in MSP were dramatically reduced after the CHC. These facts indicate that Ni/Z5A effectively catalyzed heteroatom (especially O atom) removal from MSP and hydrogenation of MSP. Naphth-1-ol and oxybis(methylene)dibenzene (OBMDB) were used as lignite-related model compounds and their CHCs were investigated to further understand the catalysis of Ni/Z5A in the CHC of MSP. As a result, Ni/Z5A proved to have 2 functions, i.e., activating H2 to biatomic active hydrogen (BAAH) and heterolytically splitting H2 to H+ relatively free from Ni/Z5A and H− adsorbed on Ni/Z5A. Over Ni/Z5A, the CHCs of naphth-1-ol and OBMDB proceeded via BAAH and H+ transfer to mainly produce tetralin and decalin from naphth-1-ol and methylcyclohexane and toluene from OBMDB.

Two-dimensional dynamic fluid bowtie attenuators

Fluence field modulated (FFM) CT allows for improvements in image quality and dose reduction. To date, only one-dimensional modulators have been proposed, as the extension to two-dimensional (2-D) modulation is difficult with solid-metal attenuation-based fluence field modulated designs. This work proposes to use liquid and gas to attenuate the x-ray beam, as unlike solids, these materials can be arranged allowing for 2-D fluence modulation. The thickness of liquid and the pressure for a given path length of gas were determined that provided the same attenuation as 30cm of soft tissue at 80, 100, 120, and 140kV. Liquid iodine, zinc chloride, cerium chloride, erbium oxide, iron oxide, and gadolinium chloride were studied. Gaseous xenon, uranium hexafluoride, tungsten hexafluoride, and nickel tetracarbonyl were also studied. Additionally, we performed a proof-of-concept experiment using a 96 cell array in which the liquid thickness in each cell was adjusted manually. Liquid thickness varied as a function of kV and chemical composition, with erbium oxide allowing for the smallest thickness. For the gases, tungsten hexaflouride required the smallest pressure to compensate for 30cm of soft tissue. The 96 cell iodine attenuator allowed for a reduction in both dynamic range to the detector and scatter-to-primary ratio. For both liquids and gases, when k-edges were located within the diagnostic energy range used for imaging, the mean beam energy exhibited the smallest change with compensation amount. The thickness of liquids and the gas pressure seem logistically implementable within the space constraints of C-arm-based cone beam CT (CBCT) and diagnostic CT systems. The gas pressures also seem logistically implementable within the space and tube loading constraints of CBCT and diagnostic CT systems.

The effect of catalyst pellet size on nickel carbonyl-induced particle sintering under low temperature CO methanation

The present work aims to evaluate the effect of catalyst pellet size on deactivation due to nickel carbonyl-induced particle sintering. For that purpose, a γ-Al2O3-supported nickel catalyst was prepared and tested under low temperature and high CO partial pressure. A total of four different pellet sizes were employed in the present study. It was found that the deactivation rate decreases with increasing pellet size. A very severe deactivation was observed when using small pellets. Large pellets exhibited instead a more stable performance. This difference in catalyst stability was explained by X-ray diffraction analyses which revealed that the growth of the nickel particles was very severe when using small pellets. An evaluation of heat and mass transfer phenomena in these four pellets was also conducted. It was found that, under the present low temperature reaction conditions, the temperature at the catalyst external surface can greatly differ from that in the bulk gas when using sufficiently large pellets. It was also shown that, for large pellets, the major part of the interior of the catalyst is exposed to negligible CO partial pressures and high temperatures, fact that can reduce the potential for nickel carbonyl formation.

Probing the microhydration of metal carbonyls: a photoelectron velocity-map imaging spectroscopic and theoretical study of Ni(CO)3(H2O)n.

A series of microhydrated nickel carbonyls, Ni(CO)3(H2O)n- (n = 0-4), are prepared via a laser vaporization supersonic cluster source in the gas phase and identified by mass-selected photoelectron velocity-map imaging spectroscopy and quantum chemical calculations. Vertical detachment energies for the n = 1-4 anions are measured from the photoelectron spectra to be 1.429 ± 0.103, 1.698 ± 0.090, 1.887 ± 0.080, and 2.023 ± 0.074 eV, respectively. The C-O stretching vibrational frequencies in the corresponding neutral clusters are determined to be 1968, 1950, 1945, and 1940 cm-1 for n = 1-4, respectively, which are characteristic of terminal CO. It is determined that the hydrogen atom of the first water molecule is bound to the nickel center. Addition of a second water molecule prefers solvation at the carbonyl terminal. Spectroscopy combined with theory suggests that the solvation of nickel tricarbonyl is dominated by a water-ring network. The present findings would have important implications for the fundamental understanding of the multifaceted mechanisms of the multibody interaction of water and carbon monoxide with transition metals.

Binuclear nickel carbonyls with the small bite chelating diphosphine ligands methylaminobis(difluorophosphine) and methylenebis(dimethylphosphine): formation of NiNi double bonds in preference to ligand cleavage

The (bid)Ni2(CO)n (n = 6, 5, 4) and (bid)2Ni(CO)n (n = 4, 3, 2) (bid = CH3N(PF2)2 and (Me2P)2CH2) species with NiNi bonds are found to be energetically favored over isomeric species with cleaved ligands in contrast to related iron carbonyl complexes.

Systematic Review of Chromium and Nickel Exposure During Pregnancy and Impact on Child Outcomes

Some forms of chromium (Cr) and nickel (Ni) are toxic, especially with chronic elevated exposure, and certain forms such as hexavalent chromium or nickel carbonyl were labeled as carcinogens. Since both metals are naturally occurring, and used in industrial processes, individuals may be exposed through ingestion of contaminated food or water, inhalation, or dermal contact. This study focused on the impact of toxic forms of Cr and Ni during pregnancy and outcomes in newborn and young children. A systematic literature review following “The Navigation Guide” was applied, and 16 reports that satisfied the inclusion criteria were scored. Six papers studied birth weight, prematurity, or gestational age: one found an association between Ni and small for gestational age, while another linked Ni with low birth weight; however, four reported no marked associations. Of six studies that examined birth defects, three found no significant associations; one noted an association between Ni and neural tube defects; one showed an association between Ni and structural birth defects; and one reported a weak effect for Cr exposure and musculoskeletal defects. In the remaining four studies, weak associations were found for hexavalent Cr and neuroblastoma, Ni and autism spectrum disorder, Cr and Ni and DNA damage, and Cr and lymphocyte damage. Among the studies that were rated as good for execution and reliability, there was weak evidence of an association between Ni and autism spectrum disorder and small for gestational age, but no significant association between Cr and a child outcome.

Excited States of the Nickel Carbonyls Ni(CO) and Ni(CO)4: Challenging Molecules for Electronic Structure Theory.

We apply a wide range of correlated electronic structure approaches to the excited states of Ni(CO)4 and Ni(CO) as model complexes of saturated and unsaturated transition metal carbonyls respectively to understand the performance of each method, in addition to setting benchmark data for these metal carbonyls. In particular, we apply the coupled-cluster linear response hierarchy, complete-active-space self-consistent field theory, N-electron valence state multireference perturbation theory, Monte Carlo configuration interaction, and time-dependent density functional theory with a range of functionals and basis sets. We find that although the systems can qualitatively be described by a single configuration, electron correlation effects are sufficiently strong to give large single amplitudes in cluster expansions, which cause spurious solutions to the response equations for the intermediate CCn methods. DFT also performs well if care is taken to choose an appropriate functional, although for Ni(CO) several popular functionals give the incorrect ground spin-state, depending on the amount of Hartree-Fock exchange.

Mechanistic Study on C–C Bond Formation of a Nickel(I) Monocarbonyl Species with Alkyl Iodides: Experimental and Computational Investigations

An open-shell reaction of the nickel(I) carbonyl species (PNP)Ni-CO (1) with iodoalkanes has been explored experimentally and theoretically. The initial iodine radical abstraction by a nickel(I) carbonyl species was suggested to produce (PNP)Ni-I (4) and the concomitant alkyl radical, according to a series of experimental indications involving stoichiometric controls employing iodoalkanes. Corresponding alkyl radical generation was also confirmed by radical trapping experiments using Gomberg’s dimer. Molecular modeling supports that the nickel acyl species (PNP)Ni-COCH3 (2) can be formed by a direct C–C bond formation between a carbonyl ligand of 1 and a methyl radical. As an alternative pathway, the five-coordinate intermediate species (PNP)Ni(CO)(CH3) (5) that involves both CO and CH3 binding at a nickel(II) center is also suggested with a comparable activation barrier, although this pathway energetically favors the formation of (PNP)Ni-CH3 (3) via a barrierless elimination of CO over a CO migratory ins...

Effects of Fe additive on diamond crystallization from carbonyl nickel powders-C system under HPHT condition**Project supported by the National Natural Science Foundation of China (Grant No. 51172089), the Natural Science Foundation of Guizhou Provincial Education Department, China (Grant No. KY [2013]183), and the Research Fund for the Doctoral Program of Tongren University, China (Grant Nos. DS1302 and trxyS1415).

In this paper, diamond crystallization from carbonyl nickel powders-C and carbonyl nickel powders+Fe–C systems are investigated in detail at a pressure of 6.0 GPa and temperatures ranging from 1410 °C–to 1435 °C by temperature gradient growth. The effects of Fe additive on the crystal morphology are discussed in the diamond crystallization process. Furthermore, Fourier infrared measurement results indicate that the spectrum of the diamond obtained from Ni + Fe–C system after annealing treatment is nearly consistent with that of natural diamond crystal. We believe that this study is of benefit to a further understanding of the growth mechanism of natural diamond.

Catalytic hydroconversion of Geting bituminous coal over FeNi–S/γ-Al2O3

FeNi/γ-Al2O3 was prepared by thermally decomposing iron pentacarbonyl and nickel tetracarbonyl onto γ-Al2O3. Geting bituminous coal (GBC) was subjected to noncatalytic hydroconversion (NCHC) and catalytic hydroconversion (CHC) in the presence of FeNi/γ-Al2O3 and sulfur at 300°C for 3h. The reaction mixtures from both NCHC and CHC were fractionated to extracts 1–5 (E1–E5) by sequential extraction. The molecular compositions of E1–E5 were characterized with a Fourier transform infrared spectrometer, gas chromatography/mass spectrometer (GC/MS), and atmospheric solid analysis probe/time of flight-mass spectrometer (ASAP/TOF-MS). The results show that the yields of E1–E5 from CHC of GBC are obviously higher than those from NCHC. According to GC/MS analysis, the group components in E1 from the CHC are dominated by alkanes, arenes, and arenols in remarkable higher yields than those from NCHC, and most of the arenes and arenols are alkyl-substituted ones. The addition of active hydrogen atoms catalytically generated over FeNi–S/γ-Al2O3 to the ipso-position of condensed aromatic rings (CARs) in GBC could play a crucial role in cleaving–CH2− and–O− linkages connected to the CARs and thereby enhanced the yields of alkylarenes and alkylarenols through CHC. Meanwhile, the partial hydrogenation of some CARs during CHC could promote the radical hydrogen transfer along with thermal rupture of some relatively strong bonds to produce soluble molecules. According to ASAP/TOF-MS analysis, the soluble species from both NCHC and CHC have molecular mass distributions ranging from 100 to 500 u. A series of polar and/or involatile organic species.