Global energy consumption is projected to increase, even in the face of substantial declines in energy intensity, at least 2-fold by midcentury relative to the present because of population and economic growth. This demand could be met, in principle, from fossil energy resources, particularly coal. However, the cumulative nature of CO2 emissions in the atmosphere demands that holding atmospheric CO2 levels to even twice their preanthropogenic values by midcentury will require invention, development, and deployment of schemes for carbon-neutral energy production on a scale commensurate with, or larger than, the entire present-day energy supply from all sources combined. Among renewable energy resources, solar energy is by far the largest exploitable resource, providing more energy in 1 hour to the earth than all of the energy consumed by humans in an entire year. In view of the intermittency of insolation, if solar energy is to be a major primary energy source, it must be stored and dispatched on demand to the end user. An especially attractive approach is to store solar-converted energy in the form of chemical bonds, i.e., in a photosynthetic process at a year-round average efficiency significantly higher than current plants or algae, to reduce land-area requirements. Scientific challenges involved with this process include schemes to capture and convert solar energy and then store the energy in the form of chemical bonds, producing oxygen from water and a reduced fuel such as hydrogen, methane, methanol, or other hydrocarbon species.

/pdf/powering-the-planet-chemical-challenges-in-solar-energy-1kb0jbsg7k.pdf

Powering the planet: Chemical challenges in solar energy utilization

3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical Routes for the Transformation of Biomass into Chemicals

We report a synthesis of highly luminescent (CdSe)ZnS composite quantum dots with CdSe cores ranging in diameter from 23 to 55 A. The narrow photoluminescence (fwhm ≤ 40 nm) from these composite dots spans most of the visible spectrum from blue through red with quantum yields of 30−50% at room temperature. We characterize these materials using a range of optical and structural techniques. Optical absorption and photoluminescence spectroscopies probe the effect of ZnS passivation on the electronic structure of the dots. We use a combination of wavelength dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, small and wide angle X-ray scattering, and transmission electron microscopy to analyze the composite dots and determine their chemical composition, average size, size distribution, shape, and internal structure. Using a simple effective mass theory, we model the energy shift for the first excited state for (CdSe)ZnS and (CdSe)CdS dots with varying shell thickness. Finally, we characterize the...

(CdSe)ZnS Core-Shell Quantum Dots - Synthesis and Characterization of a Size Series of Highly Luminescent Nanocrystallites

Nanocrystals (NCs) discussed in this Review are tiny crystals of metals, semiconductors, and magnetic material consisting of hundreds to a few thousand atoms each. Their size ranges from 2-3 to about 20 nm. What is special about this size regime that placed NCs among the hottest research topics of the last decades? The quantum mechanical coupling * To whom correspondence should be addressed. E-mail: dvtalapin@uchicago.edu. † The University of Chicago. ‡ Argonne National Lab. Chem. Rev. 2010, 110, 389–458 389

/pdf/prospects-of-colloidal-nanocrystals-for-electronic-and-3dxpyhl3r7.pdf

Prospects of Colloidal Nanocrystals for Electronic and Optoelectronic Applications

Pick your Pd partners: A number of catalytic systems have been developed for palladium-catalyzed CH activation/CC bond formation. Recent studies concerning the palladium(II)-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle are discussed (see scheme), and the versatility and practicality of this new mode of catalysis are presented. Unaddressed questions and the potential for development in the field are also addressed.

In the past decade, palladium-catalyzed CH activation/CC bond-forming reactions have emerged as promising new catalytic transformations; however, development in this field is still at an early stage compared to the state of the art in cross-coupling reactions using aryl and alkyl halides. This Review begins with a brief introduction of four extensively investigated modes of catalysis for forming CC bonds from CH bonds: PdII/Pd0, PdII/PdIV, Pd0/PdII/PdIV, and Pd0/PdII catalysis. A more detailed discussion is then directed towards the recent development of palladium(II)-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle. Despite the progress made to date, improving the versatility and practicality of this new reaction remains a tremendous challenge.

/pdf/palladium-ii-catalyzed-c-h-activation-c-c-cross-coupling-2546yox1wp.pdf

Palladium(II)-catalyzed C-H activation/C-C cross-coupling reactions: versatility and practicality.

Preparation, Structure, and Coordination Chemistry of Mo[S-2,4,6-C6H2(CHMe2)3]4.

Preparation and Characterization of Two High Oxidation State Molybdenum Dinitrogen Complexes: (MoCp*Me3)2(μ-N2) and (MoCp*Me3)(μ-N2)(WCp′Me3).

Preparation and Characterization of W(OR)4Cl2 Complexes (R: Pentafluorophenyl, 2,6-Dichlorophenyl) and Some of Their Reduction Products, Including an X-Ray Study of W(O-2,6-C6H3Cl2)4Cl(Et2O).

/pdf/an-enantiomerically-pure-adamantylimido-molybdenum-5e46ldpg4c.pdf

An Enantiomerically Pure Adamantylimido Molybdenum Alkylidene Complex. An Effective New Catalyst for Enantioselective Olefin Metathesis.

Alkylidene complexes of the type Mo(CH-t-Bu)(NAr)(OR)2 (Ar = 2, 6-diisopropylphenyl; OR = O-t-Bu, OCMe2(CF3), OCMe(CF3)2, etc.) can be prepared from a “universal precursor”, Mo(CH-t-Bu)(NAr)(triflate)2(1, 2-dimethoxyethane),1 which can be prepared in three high-yield steps from ammonium dimolybdate.2 These complexes serve as initiators for the ring opening metathesis of norbornenes and substituted norbornadienes,3 or for the polymerization of acetylenes to give polyenes,4 all in a living manner. The organic polymer can be cleaved upon treatment with an aldehyde. Norbornenes that contain a variety of organic or inorganic functionalities can be polymerized to give essentially monodisperse homopolymers and block copolymers. Recently chiral catalysts have been prepared that will polymerize norbornenes and norbornadienes stereoselectively to give all cis isotactic polymers.5 Molybdenum catalysts also have been found that will cyclopolymerize dipropargyl derivatives or substituted phenylacetylenes in a living manner.6 The stereospecific synthesis of all cis, or all trans, tactic polynorbornadienes and polynorbornenes will be discussed in detail, including a proof of tacticity.7

Living polymerization with well-defined alkylidene catalysts

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Papers

Preparation, Structure, and Coordination Chemistry of Mo[S-2,4,6-C6H2(CHMe2)3]4.

Preparation and Characterization of Two High Oxidation State Molybdenum Dinitrogen Complexes: (MoCpMe3)2(μ-N2) and (MoCpMe3)(μ-N2)(WCp′Me3).

Preparation and Characterization of W(OR)4Cl2 Complexes (R: Pentafluorophenyl, 2,6-Dichlorophenyl) and Some of Their Reduction Products, Including an X-Ray Study of W(O-2,6-C6H3Cl2)4Cl(Et2O).

An Enantiomerically Pure Adamantylimido Molybdenum Alkylidene Complex. An Effective New Catalyst for Enantioselective Olefin Metathesis.

Living polymerization with well-defined alkylidene catalysts