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At least 19 records

The metal-carbonyl bond in Ni(CO)4 and Fe(CO)5 - A clear-cut analysis

A detailed analysis of the metal-carbonyl bonding in Ni(CO)4 and Fe(CO)5, based on the newly developed contained space orbital variation (CSOV) method, is carried out to investigate various contributing factors to the interaction. Three aspects about the metal-CO interaction are presented: (1) the frozen orbital repulsion between the metal 4s and the CO is large; (2) the metal to CO pi donation is energetically much more important than the CO to the metal sigma donation; and (3) the metal 4s and 4p orbitals make a very small contribution (smaller than 0.4 eV) to the interaction energy; the largest portion of this contribution arises from the CO to metal sigma donation.

Bauschlicher, C. W., Jr.↗

A comparison of the bonding in Cr(NO)4 and Ni(CO)4

The bonding in Cr(NO)4 is very ionic, with about 1.5 electrons donated from the Cr to the NO 2pi orbitals. There is also a NO sigma donation of about 0.5 electrons to the Cr, yielding a net charge of Cr of about 1. A large MCSCF expansion is needed to describe both the ionic and covalent contributions to the Cr 3d-NO 2pi bonding. This bonding is compared to that in the isoelectronic Ni(CO)4.

Bauschlicher, C. W., Jr.↗

Bonding in zerovalent Ni compounds - NiN2 and Ni(N2)4 compared with NiCO and Ni(CO)4

Calculations are carried out on NiN2, which may be considered a prototypical metal surface-ligand system. A large Gaussian basis set and an MCPF treatment of electron correlation are used. Consideration is also given to the 2Sigma(+) states of NiN2(-), NiCO(-), and NiN2(+), the low-lying 2Delta and 2Pi states of NiN2(+), and the 1A1 states of Ni(CO)4 and Ni(N2)4.

Bauschlicher, Charles W., Jr.↗

Filled Nd(z)Fe(x)Co(4-x)Sb(12-y)Ge(y) Skutterudites: Processing and Thermoelectric Properties

Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Nd(z)Fe(x)Co(4-x)Sb(12-y)Ge(y) system has been investigated as a p-type thermoelectric material, and is stable up to 600 C. The influence of Fe and Ge content, along with filler Nd, was investigated on thermoelectric transport properties. In addition to the chemical influence on properties, some processing details of the system will also be addressed.

Thermoelectric↗

An ab initio study of Fe(CO)n, n = 1,5, and Cr(CO)6

Ab initio calculations have been performed for Cr(CO)6 and Fe(CO)n, n = 1,5. Basis sets of better than double zeta quality are used, and correlation is included using the modified coupler-pair functional method. The computed geometries and force constants are in reasonable agreement with experiment. The sequential bond dissociation energies of CO from Fe(CO)5 are estimated to be: 39, 31, 25, 22, and greater than 5 kcal/mol. It is noted that the first bond dissociation energy is relative to the singlet ground state of Fe(CO)5 and the lowest singlet state of Fe(CO)4, whereas the second is relative to the ground triplet states of Fe(CO)4 and Fe(CO)3. In addition, the binding energy for Fe-CO would be modified to 18 kcal/mol if dissociation occurred to the Fe(5F) excited state asymptote. The CO binding energies for Fe and Cr are found to be in poorer agreement with experiment than those found in a previous study on Ni(CO)4. The origins of this difference are discussed.

Barnes, Leslie A.↗

Non-Monotonic Feedback Dependence Under Abrupt Co2 Forcing Due to a North Atlantic Pattern Effect

Effective climate sensitivity (EffCS), commonly estimated from model simulations with abrupt 4×CO 2 for 150 years, has been shown to depend on the CO 2 forcing level. To understand this dependency systematically, we performed a series of simulations with a range of abrupt CO 2 forcing in two climate models. Our results indicate that normalized EffCS values in these simulations are a non-monotonic function of the CO 2 forcing, decreasing between 3× and 4×CO 2 in CESM1-LE (2× and 3×CO 2 in GISS-E2.1-G) and increasing at higher CO 2 levels. The minimum EffCS value, caused by anomalously negative radiative feedbacks, arises mainly from sea-surface temperature (SST) relative cooling in the tropical and subtropical North Atlantic. This cooling is associated with the formation of the North Atlantic Warming Hole and Atlantic Meridional Overturning Circulation collapse under CO 2 forcing. Our findings imply that understanding changes in North Atlantic SST patterns is important for constraining near-future and equilibrium global warming.

effective climate sensitivity↗

Synthesis,and structural characterization of [(CH3(C5H4N))Ga(SCH2(CO)O)]-[(4-MepyH)]+, a novel Ga(III) five coordinate complex.

The synthesis and structural characterization of a novel ionic Ga(III) five coordinate complex [{CH3(C5H4N)}Ga(SCH2(CO)O)2]-[(4-MepyH)]+, (4-Mepy = CH3(C5H5N)) from the reaction between Ga2Cl4 with sodium mercapto-acetic acid in 4-methylpyridine is described. Under basic reaction conditions the mercapto ligand is found to behave as a 2e- bidentate ligand. Single crystal X-ray diffraction studies show the complex to have a distorted square pyramidal geometry with the [(-SCH2(CO)CO-)] ligands in a trans conformation. The compound crystallizes in the P2(sub 1)/c (No. 14) space group with a = 7.7413(6) A, b = 16.744(2) A, c = 14.459(2) A, V = 1987.1(6) A(sup 3), R(F) = 0.032 and R(sub w) = 0.038.

Banger, Kulbinder K.↗

Filled Nd(sub z) Fe(sub x) Co(sub 4-x) Sb(sub 12-y) Ge(sub y) Skutterudites: Processing and Thermoelectric Properties

Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Nd (sub z) Fe (sub x) Co (sub 4-x) Sb (sub 12-y)Ge (sub y) system has been investigated as a p-type thermoelectric material, and is stable up to 600 degrees Centigrade. The influence of Fe and Ge content, along with filler Nd, was investigated on thermoelectric transport properties. In addition to the chemical influence on properties, some processing details of the system will also be addressed.

Electical Conductivity↗

Photochemical preparation of olefin addition catalysts

Novel polymer supported catalysts are prepared by photo-irradiation of low valent transition metal compounds such as Co.sub.2 (CO).sub.8, Rh.sub.4 (CO).sub.12 or Ru.sub.3 (CO).sub.12 in the presence of solid polymers containing amine ligands such as polyvinyl pyridine. Hydroformylation of olefins to aldehydes at ambient conditions has been demonstrated.

Gray, Harry B.↗

Coupling between the nickel-carbon and carbon-oxygen stretch motion in NiCO

Linear-combination-of-Gaussian-type-orbital (LCGTO) X-alpha calculations are performed on NiCO for various linear Ni-CO and NiC-O bond distances. The basis sets used are moderately large, approximately double zeta, and thus are fairly accurate within the X-alpha approximation. The electronic structure and equilibrium bond distances are consistent with recent CI calculations, indicating a much stronger Ni-CO bond than occurs in Ni(CO)4. The calculations agree to within 100/cm with the experimentally observed NiC-O stretch frequency. The Ni-CO stretch is predicted to occur at 656/cm, although at an intensity that is 640 times less. Compared with experimental results for CO adsorbed on single crystal Ni(100), the computed vibrational frequencies and intensities are less appropriate than the relevant experimental values for Ni(CO)4. This is interpreted to mean that an accurate description of the electronic structure of the nickel atom participating directly in the surface bond requires proper accounting of the bonds to its other nearest neighbors.

Dunlap, B. I.↗

Quadrennial International Ozone Symposium, Boulder, CO, August 4-9, 1980, Proceedings. Volumes 1 & 2

Recent developments in observational techniques are examined, taking into account a review of some unresolved problems in the measurement/estimation of total ozone and the vertical ozone profile, the sensitivity of Dobson total ozone estimations to wavelength band calibration uncertainties, errors in Dobson total measurements arising from aerosol attenuation, and optical stop and focussing effects in the Dobson instrument. Other subjects considered are related to total ozone observations, tropospheric ozone, upper air ozone observations, observations of trace gases in the atmosphere, ozone photochemistry and directly related photochemical models, the interaction of ozone and atmospheric circulation, ozone effects on climate, and solar activity and ozone variations. Programs and recommendations involving ozone theory and observations are also discussed, giving attention to current problems of ozone chemistry, the upper atmosphere research satellite program, a French contribution to ozone related studies, and ozone and the middle atmosphere program.

London, J.↗

Organometallic Compounds as Carriers of Extraterrestrial Cyanide in Primitive Meteorites

Extraterrestrial delivery of cyanide may have been crucial for the origin of life on Earth since cyanide is involved in the abiotic synthesis of numerous organic compounds found in extant life; however, little is known about the abundance and species of cyanide present in meteorites. Here, we report cyanide abundance in a set of CM chondrites ranging from 50 ± 1 to 2472 ± 38 nmol·g1, which relates to the degree of aqueous alteration of the meteorite and indicates that parent body processing inuenced cyanide abundance. Analysis of the Lewis Cliff 85311 meteorite shows that its releasable cyanide is primarily in the form of [FeII (CN)5(CO)]3 and [FeII(CN)4(CO)2]2-. Meteoritic delivery of iron cyanocarbonyl complexes to early Earth likely provided an important point source of free cyanide. Iron cyanocarbonyl complexes may have served as precursors to the unusual FeII(CN)(CO) moieties that form the catalytic centers of hydrogenases, which are thought to be among the earliest enzymes.

cyanide↗

On the Bonding in Fe2(CO)9

The bonding in Fe2(CO)9 is analyzed using an self consistend field (SCF) wave function for a large basis set. There is no direct Fe-Fe metal-metal bond. The bridging CO's hold the two Fe(CO)3 fragments together by a sigma donation into the empty Fe-Fe d pi orbital and metal donation from the d pi* orbital into the CO 2pi* orbital. The bonding of the terminal CO is similar to that in Ni(CO)4 and the equatorial groups in Fe(CO)5.

Bauschlicher, Charles W., Jr.↗

Correlation of Spectral and Electrochemical Properties of a Series of Ferrocene Derivatives

Charge-transfer-to-solvent (CTTS) bands are observed in the UV/VIS spectra of a series of ferrocene derivatives (ferrocene; 1,1’-dimethyl; 1,2,3,4,5-pentamethyl; 1,2,3,4,l’,2’,3’,4’-octamethyl; and decamethyl) by the addition of increasing amounts of CCl4 to ethanol solutions. A linear correlation (slope = 8540 per cm/V) was found between the redox potential and the energy of the CTTS band, consistent with electrochemical and photochemical oxidation by removal of an electron from the same molecular orbital. Inclusion of literature data for ruthenocene and [(η^(5)-C5H5)Fe(CO)]4 results in a line with a slope of 8140 per cm/V, within 1 percent of the wavenumber to electron volt conversion factor. Calculation of association constants (K) shows a slight decrease (1.2 to 0.7 per mole fraction) as the bulkiness of the cyclopentadienyl ring increases, consistent with either a steric or a repulsive electronic effect. The extinction coefficient of the CTTS absorption was constant at approximately 1700 per Mcm .

ultraviolet spectroscopy↗

Anomalous and Ungrouped Carbonaceous Chondrites in the US Antarctic Meteorite Collection and their Potential Relevance to Ryugu and Bennu

With two different carbonaceous asteroid sample return missions in full swing, attention has focused on what connections can be made between the asteroid samples and the wide range of carbonaceous chondrite meteorites in worldwide collections. The US Antarctic meteorite collection contains nearly 1000 carbonaceous chondrites of various types including many in well-established groups as well as ungrouped, unusual or anomalous groups [1]. Some of the latter have been included in, or are possibly related to, recently proposed new carbonaceous chondrite classifications – CA and CY chondrites [2,3]. In addition to these, there are numerous ungrouped samples that have properties intermediate between established groups (like CM and CO; [4]), distinct from any other groups [5], or have anomalous properties that might be attributable to parent body processes such as heating, fluid interaction, or impacts [6]. Some CM anomalous or ungrouped chondrites share spectral features with Ryugu, which has a small hydration peak arguably due to hydrated minerals left after either impact heating or shock in carbonaceous chondrites [7]. PCA 91008, PCA 02012, GRO 95566, and LEW 85311 are all CMs that have experienced heating or metamorphism that may be due to impacts, solar radiation, or radiogenic decay [6]. These samples all have low H contents, C/H (bulk), and low 17O [6,8] and may hold clues to understanding the mineralogy of Ryugu, or interpretations of its spectral properties. WIS 91600, on the other hand, appears to be related to several other highly altered CM [6], and shares properties with the newly proposed CY chondrites [6]. An understanding of this grouplet will also aid in the interpretation of Bennu samples which have strong hydration features. In addition, ungrouped carbonaceous chondrites may provide valuable insights into the aqueous alteration potentially recorded in Bennu and Ryugu samples; such as the relatively moderate aqueous alteration recognized and dated at 4-5 myr after CAIs in MAC 88107 (C2-ungrouped) by [9] to the extensive aqueous alteration apparent in MIL 090292 (C1-ungrouped) [10]. Finally, LON 94101/94102 is a brecciated CM chondrite with numerous lithologies. Its appearance is similar to some of the brecciated lithologies visible at the surface of Bennu and Ryugu [11]. Although CM chondrites with multiple lithologies are common (e.g., [12]), the lithologies are often difficult to resolve at the hand specimen scale and only after some detailed e-beam characterization are the subtle lithologic differences evident (e.g., [13]). LON 94102 contains visibly distinct clasts at the hand specimen scale, relatively rare for CM breccias. The largest CM chondrites by mass from the U.S. Antarctic meteorite collection may provide insights into the extent of brecciation and heterogeneity within more typical CM chondrite-like source asteroids. For example, recent curation CT scans [14] show possible clasts within in a subsplit of ALH 83100 (CM1/2) which is the largest CM chondrite or CM chondrite pairing group in the U.S. Antarctic collection with an original mass of 3.019 kg. Similar work on additional subsplits or meteorites may aid our understanding of heterogeneity within CM chondrites from Antarctica. Initial classification of CM chondrites in U.S. Antarctic meteorite collection includes preliminary pairing when petrographically similar CM chondrites that have been previously found in the same field area. The two largest CM chondrite preliminary pairing groups by mass are the ALH 83102 (CM2) pairing group with an original mass of 2.554 kg and the EET 96005 (CM2) pairing group with an original mass of 1.125 kg. However, preliminary pairing groups assigned at classification—intrinsically— do not include stones that are petrographically distinct. Rigorous pairing group studies of CM chondrites from specific field sites are needed to investigate if there is unrecognized heterogeneity in CM chondrites from Antarctica that may represent common asteroid impactors (pre-atmospheric entry asteroids/meteoroids). Detailed pairing studies have the potential to recognize initial stones with multiple lithologies and investigate if there are stones that only sample one of those respective lithologies in the collection. These groups of heated CMs, extensively hydrated CMs, intermediate between CM and CO chondrites, and brecciated samples are all potentially relevant to Bennu and Ryugu samples, where heating, hydration, and brecciation have all come into play. These bodies might also be comprised of material intermediate to CM and CO chondrites, or at least distinct from the well-established CC groups. These small and unusual groups of carbonaceous chondrites may help to unlock new information about early solar system processes and aid in the understanding of the evolution of these carbonaceous asteroids.

meteorites↗