A series of N-heterocyclic carbene (NHC) Ag(I) complexes have been prepared and used to study the dynamics of NHC ligand exchange in these Ag(I) complexes. These studies used solution-state variable-temperature (VT) 13 C NMR spectroscopy and the temperature-dependent changes in 13 C− 107/109 Ag coupling to determine activation energies for the ligand exchange process. The effects of concentration, bridging anions, and additives on the exchange process have been studied. The experimental activation energies for the NHC ligand exchange processes of these silver complexes are also compared with DFT calculations. The results are consistent with an associative mechanism for the Ag(I)−NHC exchange process.
The synthesis of polyisobutylene (PIB)-supported N-heterocyclic carbenes (NHCs) that are useful as ligands for recoverable/recyclable organometallic complexes is described. Both PIB-bound carbenes analogous to SIMes and IMes as well as carbene precursors bound to PIB via 1,2,3-triazoles by alkyne-azide couplings are described. Both Ag(I) and Ru(II) complexes of these carbenes are shown to be phase selectively soluble in heptane. Hoveyda-Grubbs second-generation catalysts containing a PIB-supported NHC have also been used to catalyze ring-closing metathesis.
The preparation of polyethylene-oligomer (PE(olig))-supported N-heterocyclic carbene ligands (NHCs) and their Ru complexes is described. These complexes are structurally analogous to their low molecular weight counterparts and can serve as thermomorphic, recoverable/recyclable ring-closing metathesis (RCM) catalysts. Because of the insolubility of PE(olig)-supported species at 25 °C, such complexes can perform homogeneous RCM reactions at 65 °C and, upon cooling, precipitate as solids. This allows for their quantitative separation from solutions of products.
The biased conductive probe of an atomic force microscope can induce local oxidation in ambience for converting silicon nitride films to silicon oxides with high reaction rate. Spatially resolved photoemission analysis with submicron resolution has been utilized to study the oxidation states of converted silicon oxide patterns in comparison with the surrounding Si3N4 layer. The core level shift of the Si 2p photoelectron peak and the spectral features in the valence band reveal a complete conversion of silicon nitride to silicon oxide at a bias voltage of 10 V, with no remaining nitrogen left. The major oxide is SiO2. The observed oxidation states of Si4+, Si3+, and Si2+ show a gradient depth distribution indicating excess silicon in the layer.
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