The mechanism of the ene reaction of singlet ((1)delta(g)) oxygen with simple alkenes is investigated by a combination of experimental isotope effects and several levels of theoretical calculations. For the reaction of 2,4-dimethyl-3-isopropyl-2-pentene, the olefinic carbons exhibit small and nearly equal (13)C isotope effects of 1.005-1.007, while the reacting methyl groups exhibit (13)C isotope effects near unity. In a novel experiment, the (13)C composition of the product is analyzed to determine the intramolecular (13)C isotope effects in the ene reaction of tetramethylethylene. The new (13)C and literature (2)H isotope effects are then used to evaluate the accuracy of theoretical calculations. RHF, CASSCF(10e, 8o), and restricted and unrestricted B3LYP calculations are each applied to the ene reaction with tetramethylethylene. Each predicts a different mechanism, but none leads to reasonable predictions of the experimental isotope effects. It is concluded that none of these calculations accurately describe the reaction. A more successful approach was to use high-level, up to CCSD(T), single-point energy calculations on a grid of B3LYP geometries. The resulting energy surface is supported by its accurate predictions of the intermolecular (13)C and (2)H isotope effects and a very good prediction of the reaction barrier. This CCSD(T)//B3LYP surface features two adjacent transition states without an intervening intermediate. This is the first experimentally supported example of such a surface and the first example of a valley-ridge inflection with significant chemical consequences.

The intramolecular H/D kinetic isotope effect in the ene reaction of singlet oxygen with tetramethylethylene is studied using quasiclassical direct dynamics calculations on a B3LYP/6-31G* potential energy surface. Starting from the area of the energy surface around a valley-ridge inflection point, random trajectories lead to predominantly H abstraction over D abstraction, despite the symmetry of the surface and the absence of a barrier to either reaction. This demonstrates a new form of kinetic isotope effect, unrelated to the usual effect of zero-point energies on barriers. Dynamics calculations on the reaction of cis-2-pentene predict the experimentally observed mixture of regioisomeric products, while the minimum-energy path leads to only one product. For energy surfaces containing two adjacent saddle points, dynamics effects are important for understanding both product and isotopic selectivity, and this should be considered in the interpretation of experimental results.

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Recent synthesis and NMR spectroscopy of neutral Ir(V) complexes hydridotris(3,5-dimethylpyrazol-1-yl)borato tetrahydride (Tp*IrH(4)) and hydridotris(pyrazol-1-yl)borato tetrahydride (TpIrH(4)) have been interpreted as supporting face-capped octahedral structures (C(3upsilon)) with each of three Ir-H bonds trans to an Ir-N bond and the fourth hydride capping the IrH(3) face. Here, density functional geometry optimizations and coupled cluster calculations on hydridotris(pyrazol-1-yl)borato iridium tetrahydrogen find that a C(s) edge-bridged octahedral tetrahydride structure and a C(1) eta(2)-dihydrogen, dihydride structure are local minima and find that the C(3upsilon) structure is a local maximum (second-order saddle point). Several low energy transition states connecting the local minima have been located, and these minima can be used to simulate the experimental NMR spectra. A comparison of the experimental infrared spectrum of Tp*IrH(4) and the harmonic frequency calculations on the C(s), C(1), and C(3upsilon) structures also supports the assignment of the C(s)and C(1) structures as the observed ones.

The mechanism of the epoxidation of 2-cyclohexen-1-one with tert-butyl hydroperoxide mediated by DBU was studied by a combination of experimental kinetic isotope effects and theoretical calculations. A large 12 C/ 13 C (k 12 C /k 13 C ) isotope effect of ≈1.032 was observed at the C 3 (β) position of cyclohexenone, while a much smaller 12 C/ 13 C isotope effect of 1.010 was observed at the C 2 (α) position. Qualitatively, these results are indicative of nucleophilic addition to the enone being the rate-limiting step. Theoretical calculations support this interpretation. Transition structures for the addition step lead to predicted isotope effects that approximate the experimental values, while the predicted isotope effects for the ring-closure step are not consistent with experiment. The calculations correctly favor a rate-limiting addition step, but suggest that the barriers for the addition and ringclosure steps are crudely similar in energy. The stereochemistry of these epoxidations is predicted to be governed by a preference for an initial axial addition, and the role of this preference in experimental diastereoselectivity observations is discussed.

A multitude of challenges exist when cementing production liners for deepwater operations. In many platform operations, cutting windows to sidetrack and drill highly deviated well paths to intersect reservoir targets result in difficulty obtaining adequate casing standoff due to tight inside diameter (ID) restrictions from previous casing architecture. Many of the zones near the target interval may have significant pressure depletion which can lead to expensive Synthetic Based Mud (SBM) losses and associated non-productive time (NPT). The size of the production liner is dependent on the wellbore architecture and completion plan. Thus in most cases, the borehole must be under-reamed in order to provide for adequate cement sheath thickness. In these cases, centralizer selection and placement can be challenging or all together impractical. Cementing in SBM environments has also been traditionally more challenging because special considerations for spacer/surfactant/mud design and testing are required to effectively displace the mud and "water-wet" the formation/casing for good quality cement-bonding. Technology improvements in spacer and surfactant package formulations provide a more qualitative method for optimum surfactant design to maximize mud removal and provide a bonding surface to the formation. Liner hanger selection may not always provide the capability for pipe rotation which has shown to be very effective for mud removal and increased circumferential cement coverage. Without pipe rotation, additional key techniques for successful cementation must be prioritized. A process driven decision matrix is presented along with a recent selection of successful production liners to support the design concept.