The covalent diamantyl (CH) and oxadiamantyl (CHO) dimers are stabilized by London dispersion attractions between the dimer moieties. Their solid-state and gas-phase structures were studied using a multitechnique approach, including single-crystal X-ray diffraction (XRD), gas-phase electron diffraction (GED), a combined GED/microwave (MW) spectroscopy study, and quantum chemical calculations. The inclusion of medium-range electron correlation as well as the London dispersion energy in density functional theory is essential to reproduce the experimental geometries. The conformational dynamics computed for CHO agree well with solution NMR data and help in the assignment of the gas-phase MW data to individual diastereomers. Both in the solid state and the gas phase the central C-C bond is of similar length for the diamantyl [XRD, 1.642(2) Å; GED, 1.630(5) Å] and the oxadiamantyl dimers [XRD, 1.643(1) Å; GED, 1.632(9) Å; GED+MW, 1.632(5) Å], despite the presence of two oxygen atoms. Out of a larger series of quantum chemical computations, the best match with the experimental reference data is achieved with the PBEh-3c, PBE0-D3, PBE0, B3PW91-D3, and M06-2X approaches. This is the first gas-phase confirmation that the markedly elongated C-C bond is an intrinsic feature of the molecule and that crystal packing effects have only a minor influence.
Oxadiamondoids representing a new class of carbon nanoparticles were prepared from the respective diamondoid ketones via an effective two-step procedure involving addition of methyl magnesium iodide and oxidation with trifluoroperacetic acid in trifluoroacetic acid. The reactivities of the oxacages are determined by the position of the dopant and are in good agreement with computational predictions.
Nanometer-sized doubly bonded diamondoid dimers and trimers, which may be viewed as models of diamond with surface sp(2)-defects, were prepared from corresponding ketones via a McMurry coupling and were characterized by spectroscopic and crystallographic methods. The neutral hydrocarbons and their radical cations were studied utilizing density functional theory (DFT) and ab initio (MP2) methods, which reproduce the experimental geometries and ionization potentials well. The van der Waals complexes of the oligomers with their radical cations that are models for the self-assembly of diamondoids, form highly delocalized and symmetric electron-deficient structures. This implies a rather high degree of σ-delocalization within the hydrocarbons, not too dissimilar to delocalized π-systems. As a consequence, sp(2)-defects are thus also expected to be nonlocal, thereby leading to the observed high surface charge mobilities of diamond-like materials. In order to be able to use the diamondoid oligomers for subsequent surface attachment and modification, their C-H-bond functionalizations were studied, and these provided halogen and hydroxy derivatives with conservation of unsaturation.
The
convenient and scalable preparative approach for the two-step
α-methylation of ketones is described. The optimized protocols
for regioselective preparation of enaminones with further diastereoselective
and functional groups tolerant hydrogenation to α-methylketones
are developed. The scope and limitations of the proposed methodology
are discussed. The advantages compared to known procedures are demonstrated.
The unexpected role of acetone in the hydrogenation is suggested.
The evaluation of the method for both early building block synthesis
and late-stage CH-functionalization is shown. The elaborate procedures’ preparability and scalability are
demonstrated by the synthesis of several α-methyl ketones up
to 100 g amount.
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