Synthetic, structural and mechanistic studies of interactions of carbon, nitrogen, and oxygen nucleophiles with bis-pentamethylcyclopentadienyl zirconium and hafnium derivatives

The reactivity of permethylzirconocene and permethylhafnocene complexes with various nucleophiles has been investigated. Permethylzirconocene reacts with sterically hindered ketenes and allenes to afford metallacycle products. Reaction of these cummulenes with permethylzirconocene hydride complexes affords enolate and σ-allyl species, respectively. Reactions which afford enolate products are nonstereospecific, whereas reactions which afford allyl products initially give a cis-σ-allyl complex which rearranges to its trans isomer. The mechanism of these reactions is proposed to occur either by a Lewis Acid-Lewis Base interaction (ketenes) or by formation of a π-olefin intermediate (allenes).

Permethylzirconocene haloacyl complexes react with strong bases such as lithium diisopropylamide or methylene trimethylphosphorane to afford ketene compounds. Depending on the size of the alkyl ketene substituent, the hydrogenation of these compounds affords enolate-hydride products with varying degrees of stereoselectivity. The larger the substituent, the greater is the selectivity for cis hydrogenation products.

The reaction of permethylzirconocene dihydride and permethylhafnocene dihydride with methylene trimethylphosphorane affords methyl-hydride and dimethyl derivatives. Under appropriate conditions, the metallated-ylide complex 1, (η^5-C_5(CH_3)_5)_2 Zr(H)CH_2PMe_2CH_2, is also obtained and has been structurally characterized by X-ray diffraction techniques. Reaction of 1 with CO affords (η^5-C_5(CH_3)_5)_2 Zr(C,O-η^2 -(PMe_3)HC=CO)H which exists in solution as an equilibrium mixture of isomers. In one isomer (2), the η^2-acyl oxygen atom occupies a lateral equatorial coordination position about zirconium, whereas in the other isomer (3), the η-acyl oxygen atom occupies the central equatorial position. The equilibrium kinetics of the 2→3 isomerization have been studied and the structures of both complexes confirmed by X-ray diffraction methods. These studies suggest a mechanism for CO insertion into metal-carbon bonds of the early transition metals.

Permethylhafnocene dihydride and permethylzirconocene hydride complexes react with diazoalkanes to afford η^2-N, N' -hydrazonido species in which the terminal nitrogen atom of the diazoalkane molecule has inserted into a metal-hydride or metal-carbon bond. The structure of one of these compounds, Cp*_2Zr(NMeNCTol_2)OH, has been determined by X-ray diffraction techniques. Under appropriate conditions, the hydrazonido-hydride complexes react with a second equivalent of diazoalkene to afford η' -N-hydrazonido-η^2-N, N' -hydrazonido species.

Spatial filtering in tone reproduction and vision

This thesis is concerned with spatial filtering. What is its utility in tone reproduction? Does it exist in vision, and if so, what constraints does it impose on the nervous system?

Tone reproduction is just the art and science of taking a picture and then displaying it. The sensors available to capture an image have a greater dynamic range than the media that may be used to display it. Conventionally, spatial filtering is used to boost contrast; it ameliorates the loss of contrast that results when the sensor signal range is scaled down to fit the display range. In this thesis, a type of nonlinear spatial filtering is discussed that results in direct range reduction without range scaling. This filtering process is instantiated in a real-time image processor built using analog CMOS VLSI.

Spatial filtering must be applied with care in both artificial and natural vision systems. It is argued that the nervous system does not simply filter linearly across an image. Rather, the way that we see things implies that the nervous system filters nonlinearly. Further, many models for color vision include a high-pass filtering step in which the DC information is lost. A real-time study of filtering in color space leads to the conclusion that the nervous system is not that simple, and that it maintains DC information by referencing to white.

Using climate extension to assist coastal decision-makers with climate adaptation

Coastal managers need accessible, trusted, tailored resources to help them interpret climate information, identify vulnerabilities, and apply climate information to decisions about adaptation on regional and local levels. For decades, climate scientists have studied the impacts that short term natural climate variability and long term climate change will have on coastal systems. For example, recent estimates based on Intergovernmental Panel on Climate Change (IPCC) warming scenarios suggest that global sea levels may rise 0.5 to 1.4 meters above 1990 levels by 2100 (Rahmstorf 2007; Grinsted, Moore, and Jevrejeva 2009). Many low-lying coastal ecosystems and communities will experience more frequent salt water intrusion events, more frequent coastal flooding, and accelerated erosion rates before they experience significant inundation. These changes will affect the ways coastal managers make decisions, such as timing surface and groundwater withdrawals, replacing infrastructure, and planning for changing land use on local and regional levels. Despite the advantages, managers’ use of scientific information about climate variability and change remains limited in environmental decision-making (Dow and Carbone 2007). Traditional methods scientists use to disseminate climate information, like peer-reviewed journal articles and presentations at conferences, are inappropriate to fill decision-makers’ needs for applying accessible, relevant climate information to decision-making. General guides that help managers scope out vulnerabilities and risks are becoming more common; for example, Snover et al. (2007) outlines a basic process for local and state governments to assess climate change vulnerability and preparedness. However, there are few tools available to support more specific decision-making needs. A recent survey of coastal managers in California suggests that boundary institutions can help to fill the gaps between climate science and coastal decision-making community (Tribbia and Moser 2008). The National Sea Grant College Program, the National Oceanic and Atmospheric Administration's (NOAA) university-based program for supporting research and outreach on coastal resource use and conservation, is one such institution working to bridge these gaps through outreach. Over 80% of Sea Grant’s 32 programs are addressing climate issues, and over 60% of programs increased their climate outreach programming between 2006 and 2008 (National Sea Grant Office 2008). One way that Sea Grant is working to assist coastal decision-makers with using climate information is by developing effective methods for coastal climate extension. The purpose of this paper is to discuss climate extension methodologies on regional scales, using the Carolinas Coastal Climate Outreach Initiative (CCCOI) as an example of Sea Grant’s growing capacities for climate outreach and extension. (PDF contains 3 pages)