Linear Inverse Sandwich Complexes of Tetraanionic Benzene Stabilized by Covalent δ-Bonding with Late Lanthanides.

A series of dilanthanide benzene inverse sandwich complexes of the type (CpLn)(μ-η:η-CH) () (Ln = Y, Gd, Tb, Dy, Tm) are reported. These compounds are synthesized by reduction of the respective trivalent dimers CpLnI (Ln = Y, Gd, Tb, Dy, Tm) in diethyl ether with potassium graphite in the presence of benzene, and they feature an unusual linear coordination geometry with a highly planar benzene bridge as verified by single-crystal X-ray diffraction. The Ln-Bz distances of are the shortest distances observed to date, ranging from 1.

Metal-Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (Cp)UX (X = Cl, Br, I) Clusters.

The actinide elements are attractive alternatives to transition metals or lanthanides for the design of exchange-coupled multinuclear single-molecule magnets. However, the synthesis of such compounds is challenging, as is unraveling any contributions from exchange coupling to the overall magnetism. To date, only a few actinide compounds have been shown to exhibit exchange coupling and single-molecule magnetism.

Coercive Fields Exceeding 30 T in the Mixed-Valence Single-Molecule Magnet (Cp)HoI.

Mixed-valence dilanthanide complexes of the type (Cp)LnI (Cp = pentaisopropylcyclopentadienyl; Ln = Gd, Tb, Dy) featuring a direct Ln-Ln σ-bonding interaction have been shown to exhibit well-isolated high-spin ground states and, in the case of the Tb and Dy variants, a strong axial magnetic anisotropy that gives rise to a large magnetic coercivity. Here, we report the synthesis and characterization of two new mixed-valence dilanthanide compounds in this series, (Cp)LnI (; Ln = Ho, Er). Both compounds feature a Ln-Ln bonding interaction, the first such interaction in any molecular compounds of Ho or Er.

Recovery of Isoamyl Alcohol by Graphene Oxide Immobilized Membrane and Air-Sparged Membrane Distillation.

Isoamyl alcohol is an important biomass fermentation product that can be used as a gasoline surrogate, jet fuel precursor, and platform molecule for the synthesis of fine chemicals and pharmaceuticals. This study reports on the use of graphene oxide immobilized membra (GOIMs) for the recovery of isoamyl alcohol from an aqueous matrix. The separation was performed using air-sparged membrane distillation (ASMD).

A Trinuclear Gadolinium Cluster with a Three-Center One-Electron Bond and an = 11 Ground State.

The recent discovery of metal-metal bonding and valence delocalization in the dilanthanide complexes (Cp)LnI (Cp = pentaisopropylcyclopentadienyl; Ln = Y, Gd, Tb, Dy) opened up the prospect of harnessing the 4f5d electron configurations of non-traditional divalent lanthanide ions to access molecules with novel bonding motifs and magnetism. Here, we report the trinuclear mixed-valence clusters (Cp)LnHI (, Ln = Y, Gd), which were synthesized via potassium graphite reduction of the trivalent clusters (Cp)LnHI. Structural, computational, and spectroscopic analyses support valence delocalization in resulting from a three-center, one-electron σ bond formed from the 4d and 5d orbitals on Y and Gd, respectively.

Solvent-free dehydration, cyclization, and hydrogenation of linalool with a dual heterogeneous catalyst system to generate a high-performance sustainable aviation fuel.

The development of efficient catalytic methods for the synthesis of bio-based, full-performance jet fuels is critical for limiting the impacts of climate change while enabling a thriving modern society. To help address this need, here, linalool, a terpene alcohol that can be produced via fermentation of biomass sugars, was dehydrated, cyclized, and hydrogenated in a one-pot reaction under moderate reaction conditions. This sequence produced a biosynthetic fuel mixture primarily composed of 1-methyl-4-isopropylcyclohexane (p-menthane) and 2,6-dimethyloctane (DMO).

Divalent Lanthanide Metallocene Complexes with a Linear Coordination Geometry and Pronounced 6s-5d Orbital Mixing.

A small but growing number of molecular compounds have been isolated featuring divalent lanthanides with 4f5d electron configurations. While the majority of these possess trigonal coordination geometries, we previously reported the first examples of linear divalent metallocenes Ln(Cp) (Ln = Tb, Dy; Cp = pentaisopropylcyclopentadienyl). Here, we report the synthesis and characterization of the remainder of the Ln(Cp) () series (including Y and excluding Pm).

Ultrahard magnetism from mixed-valence dilanthanide complexes with metal-metal bonding.

Magnetic effects of lanthanide bonding Lanthanide coordination compounds have attracted attention for their persistent magnetic properties near liquid nitrogen temperature, well above alternative molecular magnets. Gould . report that introducing metal-metal bonding can enhance coercivity.

Bio-Based Cycloalkanes: The Missing Link to High-Performance Sustainable Jet Fuels.

Invited for this month's cover is the group of Ben Harvey at the Naval Air Warfare Center, Weapons Division, China Lake. The image shows several examples of bio-based cycloalkanes that have been developed as next-generation sustainable jet fuels. The Review itself is available at 10.

Synthesis of Bio-Based Methylcyclopentadiene from 2,5-Hexanedione: A Sustainable Route to High Energy Density Jet Fuels.

The sustainable, bio-based, platform chemical, 2,5-hexanedione [HD (1)], was efficiently converted to methylcyclopentadiene [MCPD (4)] through a three-step process consisting of intramolecular aldol condensation, catalytic chemoselective hydrogenation, and dehydration. Base-catalyzed aldol condensation of 1 resulted in the formation of 3-methyl-2-cyclopenten-1-one [MCO (2)], which was then converted to 3-methyl-2-cyclopenten-1-ol [MCP (3)] by chemoselective reduction with a ternary Ru catalyst system [RuCl (PPh ) /NH (CH ) NH /KOH]. The hydrogenation proceeded with 96 % chemoselectivity.

Bio-Based Cycloalkanes: The Missing Link to High-Performance Sustainable Jet Fuels.

The development of sustainable energy solutions that reduce global carbon emissions, while maintaining high living standards, is one of the grand challenges of the current century. Transportation fuels are critical to economic development, globalization, and the advancement of society. Although ground vehicles and small aircraft are beginning a slow transition toward electric propulsion with energy sourced from solar radiation or wind, the extreme power requirements of jet aircraft require a more concentrated source of energy that is conveniently provided by liquid hydrocarbon fuels.

[4+4]-Cycloaddition of Isoprene for the Production of High-Performance Bio-Based Jet Fuel.

Isoprene was efficiently converted to 1,6-dimethyl-1,5-cyclooctadiene (DMCOD) by selective [4+4]-cycloaddition with a catalyst formed by in situ reduction of [(PI)FeCl(μ-Cl)] (PI = [2-(2,6-(CH)-CH-N=C(CH))-CHN]). DMCOD was isolated in 92% yield, at the preparative scale, with a catalyst loading of 0.025 mol%, and a TON of 3680.

Synthesis and Magnetism of Neutral, Linear Metallocene Complexes of Terbium(II) and Dysprosium(II).

The divalent metallocene complexes Ln(Cp) (Ln = Tb, Dy) were synthesized through the KC reduction of Ln(Cp)I intermediates and represent the first examples of neutral, linear metallocenes for these elements. X-ray diffraction analysis, density functional theory calculations, and magnetic susceptibility measurements indicate a 4f5d electron configuration with strong s/d mixing that supports the linear coordination geometry. A comparison of the magnetic relaxation behavior of the two divalent metallocenes relative to salts of their trivalent counterparts, [Ln(Cp)][B(CF)], reveals that lanthanide reduction has opposing effects for dysprosium and terbium, with magnetic relaxation times increasing from Tb to Tb and decreasing from Dy to Dy.

High-Performance Jet Fuels Derived from Bio-Based Alkenes by Iron-Catalyzed [2+2] Cycloaddition.

A series of high-performance cycloparaffinic fuels have been generated by [2+2] cycloaddition of the bio-derived alkenes 1-hexene, isoprene, and 1-pentene, catalyzed by a low-valent iron pyridine(diimine) complex [( PDI)Fe(N ) (μ-N )] [ PDI=N,N'-(2,6-pyridinediyldiethylidyne)bis(2,6-dimethylbenzenamine)]. Reactions with 1-pentene and 1-hexene resulted in 85 % selectivity to 1,2-cyclobutanes, and 12 % selectivity to acyclic alkenes generated by β-hydride elimination. Self-dimerization of isoprene was sluggish and generated heavier oligomer products, but cross-dimerization of isoprene with 1-hexene afforded primarily a 1,3-cyclobutane product, along with isomers of acyclic C mixed dimers.

High-temperature magnetic blocking and magneto-structural correlations in a series of dysprosium(iii) metallocenium single-molecule magnets.

A series of dysprosium(iii) metallocenium salts, [Dy(Cp)][B(CF)] (R = H (), Me (), Et (), iPr ()), was synthesized by reaction of DyI with the corresponding known NaCp (R = H, iPr) and novel NaCp (R = Me, Et) salts at high temperature, followed by iodide abstraction with [H(SiEt)][B(CF)]. Variation of the substituents in this series results in substantial changes in molecular structure, with more sterically-encumbering cyclopentadienyl ligands promoting longer Dy-C distances and larger Cp-Dy-Cp angles. Dc and ac magnetic susceptibility data reveal that these structural changes have a considerable impact on the magnetic relaxation behavior and operating temperature of each compound.

Experimental Data Extraction and in Silico Prediction of the Estrogenic Activity of Renewable Replacements for Bisphenol A.

Bisphenol A (BPA) is a ubiquitous compound used in polymer manufacturing for a wide array of applications; however, increasing evidence has shown that BPA causes significant endocrine disruption and this has raised public concerns over safety and exposure limits. The use of renewable materials as polymer feedstocks provides an opportunity to develop replacement compounds for BPA that are sustainable and exhibit unique properties due to their diverse structures. As new bio-based materials are developed and tested, it is important to consider the impacts of both monomers and polymers on human health.

Renewable Gasoline, Solvents, and Fuel Additives from 2,3-Butanediol.

2,3-Butanediol (2,3-BD) is a renewable alcohol that can be prepared in high yield from biomass sugars. 2,3-BD was selectively dehydrated in a solvent-free process to a complex mixture of 2-ethyl-2,4,5-trimethyl-1,3-dioxolanes and 4,5-dimethyl-2isopropyl dioxolanes with the heterogeneous acid catalyst Amberlyst-15. The purified dioxolane mixture exhibited an anti-knock index of 90.

A high-performance renewable thermosetting resin derived from eugenol.

A renewable bisphenol, 4,4'-(butane-1,4-diyl)bis(2-methoxyphenol), was synthesized on a preparative scale by a solvent-free, Ru-catalyzed olefin metathesis coupling reaction of eugenol followed by hydrogenation. After purification, the bisphenol was converted to a new bis(cyanate) ester by standard techniques. The bisphenol and cyanate ester were characterized rigorously by NMR spectroscopy and single-crystal X-ray diffraction studies.

High-density biosynthetic fuels: the intersection of heterogeneous catalysis and metabolic engineering.

Biosynthetic valencene, premnaspirodiene, and natural caryophyllene were hydrogenated and evaluated as high performance fuels. The parent sesquiterpenes were then isomerized to complex mixtures of hydrocarbons with the heterogeneous acid catalyst Nafion SAC-13. High density fuels with net heats of combustion ranging from 133-141 000 Btu gal(-1), or up to 13% higher than commercial jet fuel could be generated by this approach.

Synthesis, characterization, and cure chemistry of renewable bis(cyanate) esters derived from 2-methoxy-4-methylphenol.

A series of renewable bis(cyanate) esters have been prepared from bisphenols synthesized by condensation of 2-methoxy-4-methylphenol (creosol) with formaldehyde, acetaldehyde, and propionaldehyde. The cyanate esters have been fully characterized by infrared spectroscopy, (1)H and (13)C NMR spectroscopy, and single crystal X-ray diffraction. These compounds melt from 88 to 143 °C, while cured resins have glass transition temperatures from 219 to 248 °C, water uptake (96 h, 85 °C immersion) in the range of 2.

Synthesis of renewable bisphenols from creosol.

A series of renewable bisphenols has been synthesized from creosol (2-methoxy-4-methylphenol) through stoichiometric condensation with short-chain aldehydes. Creosol can be readily produced from lignin, potentially allowing for the large scale synthesis of bisphenol A replacements from abundant waste biomass. The renewable bisphenols were isolated in good yields and purities without resorting to solvent-intense purification methods.

Charge density analysis of the (C-C)-->Ti agostic interactions in a titanacyclobutane complex.

The experimental electron density study of Ti(C(5)H(4)Me)(2)[(CH(2))(2)CMe(2)] provides direct evidence for the presence of (C-C)-->Ti agostic interactions. In accord with the model of Scherer and McGrady, the C(alpha)-C(beta) bond densities no longer show cylindrical symmetry in the vicinity of the Ti atom and differ markedly from those of the other C-C bonds. At the points along the C(alpha)-C(beta) bond where the deviation is maximal the electron density is elongated toward the metal center.

Structural and spectroscopic demonstration of agostic C-C interactions in electron-deficient metallacyclobutanes and related cage complexes: possible implications for olefin polymerizations and metatheses.

The reaction of the half-open titanocene, Ti(C5H5)(c-C8H11)(PMe3) (c-C8H11 = cyclooctadienyl), with two equivalents of PhC2SiMe3 leads to their incorporation and coupling to the dienyl fragment. One alkyne inserts into a C-H bond of the central CH2 group of the c-C8H11 ligand's edge-bridge, while the second undergoes a 5+2 coupling with the dienyl fragment, yielding coordinated sigma-allyl and olefin fragments, as demonstrated by X-ray diffraction. Together with the C5H5 and PMe3 coordinations, this leads to a 14-electron count.

Reactions of SF6 with organotitanium and organozirconium complexes: the "inert" SF6 as a reactive fluorinating agent.

The normally remarkably inert SF6 has been found to be quite reactive toward low valent organometallic compounds, under conditions in which usually powerful fluorinating agents may be less reactive. Reaction of SF6 with Ti[1,3-C5H3(t-Bu)2](6,6-dmch)(PMe3), for example, leads to {Ti[1,3-C5H3(t-Bu)2]F2}4 (dmch = dimethylcyclohexadienyl), whose structure is based on a cube of fluoride ions with the ligated titanium centers situated above four coplanar face centers.