21 research outputs found
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The mechanism for iron-catalyzed alkene isomerization in solution
Here we report nano- through microsecond time-resolved IR experiments of iron-catalyzed alkene isomerization in room-temperature solution. We have monitored the photochemistry of a model system, Fe(CO){sub 4}({eta}{sup 2}-1-hexene), in neat 1-hexene solution. UV-photolysis of the starting material leads to the dissociation of a single CO to form Fe(CO){sub 3}({eta}{sup 2}-1-hexene), in a singlet spin state. This CO loss complex shows a dramatic selectivity to form an allyl hydride, HFe(CO){sub 3}({eta}{sup 3}-C{sub 6}H{sub 11}), via an internal C-H bond-cleavage reaction in 5-25 ns. We find no evidence for the coordination of an alkene molecule from the bath to the CO loss complex, but do observe coordination to the allyl hydride, indicating that it is the key intermediate in the isomerization mechanism. Coordination of the alkene ligand to the allyl hydride leads to the formation of the bis-alkene isomers, Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) and Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2}. Because of the thermodynamic stability of Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) over Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2} (ca. 12 kcal/mol), nearly 100% of the alkene population will be 2-alkene. The results presented herein provide the first direct evidence for this mechanism in solution and suggest modifications to the currently accepted mechanism
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Direct observation of photoinduced bent nitrosyl excited-state complexes
Ground state structures with side-on nitrosyl ({eta}{sup 2}-NO) and isonitrosyl (ON) ligands have been observed in a variety of transition-metal complexes. In contrast, excited state structures with bent-NO ligands have been proposed for years but never directly observed. Here we use picosecond time-resolved infrared spectroscopy and density functional theory (DFT) modeling to study the photochemistry of Co(CO){sub 3}(NO), a model transition-metal-NO compound. Surprisingly, we have observed no evidence for ON and {eta}{sup 2}-NO structural isomers, but have observed two bent-NO complexes. DFT modeling of the ground and excited state potentials indicates that the bent-NO complexes correspond to triplet excited states. Photolysis of Co(CO){sub 3}(NO) with a 400-nm pump pulse leads to population of a manifold of excited states which decay to form an excited state triplet bent-NO complex within 1 ps. This structure relaxes to the ground triplet state in ca. 350 ps to form a second bent-NO structure
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Ligand Rearrangement Reactions of Cr(CO)6 in Alcohol Solutions: Experiment and Theory
The ligand rearrangement reaction of Cr(CO)6 is studied in a series of alcohol solutions using ultafast, infrared spectroscopy and Brownian dynamics simulations
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The nature and role of bridged carbonyl intermediates in the ultrafast photo-induced rearrangement of Ru3(CO)12.
The photochemistry of the trimetal cluster,Ru(3)(CO)12, was investigated on the ultrafast timescale using UV-vis pump, infrared probe spectroscopy in order to study the transient intermediates formed upon photoexcitation
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The nature and role of bridged carbonyl intermediates in the ultrafast photo-induced rearrangement of Ru3(CO)12.
The photochemistry of the trimetal cluster,Ru(3)(CO)12, was investigated on the ultrafast timescale using UV-vis pump, infrared probe spectroscopy in order to study the transient intermediates formed upon photoexcitation
Thermodynamic Study on Dynamic Water Vapor Sorption in Sylgard-184
The dynamic and equilibrium water vapor sorption properties
of
Sylgard-184, a commercially available polyÂ(dimethylsiloxane) elastomer
(PDMS), were determined via gravimetric analysis from 30 to 70 °C.
Described here is a methodology for quantitatively assessing how water
vapor diffuses and ad/absorbs into polymeric materials that are traditionally
considered hydrophobic. PDMS materials are frequently chosen for their
moisture barrier properties; our results, however, demonstrate that
moisture is able to penetrate the material over a range of temperatures
and humidities. The sorption values measured here ranged from ca.
0.1 to 1.4 cm<sup>3</sup> (STP) H<sub>2</sub>O/g Sylgard. The isotherms
exhibited sigmoidal character and were fit to a triple mode sorption
model. Asymptotic behavior at low water activities was characterized
using a Langmuir type adsorption model, linear behavior was fit to
a Henry’s law type dependence, and the convex portion at higher
activities was fit with good agreement to Park’s equation for
pooling or clustering. The thermal dependence of these sorption modes
was also explored and reported. The dynamics of the sorption process
were fit to a Fickian model and effective diffusivities are reported
along with corresponding activation energies. The diffusivity values
measured here ranged from ca. 0.5 to 3.5 × 10<sup>–5</sup> cm<sup>2</sup>/s depending on the temperature and relative humidity.
The concentration dependence of the diffusivity showed a direct correlation
with the three modes of uptake obtained from the isotherms. Corrections
to the diffusivities were calculated using existing models that take
into account adsorption and pooling
Deflagration Rate Measurements of Three Insensitive High Explosives: LLM-105, TATB, and DAAF Deflagration Rate Measurements of Three Insensitive High Explosives: LLM-105, TATB, and DAAF
Abstract. The pressure dependent deflagration rates of LLM-105, DAAF and TATB based formulations were measured in the LLNL high pressure strand burner. The role of binder amount, explosive type, and thermal damage and their effects on the deflagration rate will be discussed. One DAAF formulation, two different formulations of LLM-105, and four formulations of TATB were studied; results indicate that binder amount and type play a minor role in the deflagration behavior. This is in sharp contrast to the HMX based formulations which strongly depend on binder amount and type. The effect of preheating these samples was considerably more dramatic. In the case of LLM-105, preheating the sample appears to have little effect on the deflagration rate. In contrast, preheating DAAF and TATB formulations causes the deflagration rate to accelerate. The thermal and mechanical properties of these formulations will be discussed in the context of their pressure and temperature dependent deflagration rates