Transition metal-alkane complexes-termed σ-complexes because the alkane donates electron density to the metal from a σ-symmetry carbon-hydrogen (C-H) orbital-are key intermediates in catalytic C-H activation processes, yet these complexes remain tantalizingly elusive to characterization in the solid state by single-crystal x-ray diffraction techniques. Here, we report an approach to the synthesis and characterization of transition metal-alkane complexes in the solid state by a simple gas-solid reaction to produce an alkane σ-complex directly. This strategy enables the structural determination, by x-ray diffraction, of an alkane (norbornane) σ-bound to a d(8)-rhodium(I) metal center, in which the chelating alkane ligand is coordinated to the pseudosquare planar metal center through two σ-C-H bonds.

The two-coordinate cationic Ni(I) bis-N-heterocyclic carbene complex [Ni(6-Mes)2]Br (1) [6-Mes =1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene] has been structurally characterized and displays a highly linear geometry with a C-Ni-C angle of 179.27(13)°. Density functional theory calculations revealed that the five occupied metal-based orbitals are split in an approximate 2:1:2 pattern. Significant magnetic anisotropy results from this orbital degeneracy, leading to single-ion magnet (SIM) behavior.

The reaction of the hydride cluster [W3S4H3(dmpe)3]+ (1, dmpe=1,2‐bis(dimethylphosphanyl)ethane) with acids (HCl, CF3COOH, HBF4) in CH2Cl2 solution under pseudo‐first‐order conditions of excess acid occurs with three kinetically distinguishable steps that can be interpreted as corresponding to successive formal substitution processes of the coordinated hydrides by the anion of the acid (HCl, CF3COOH) or the solvent (HBF4). Whereas the rate law for the third step changes with the nature of the acid, the first two kinetic steps always show a second‐order dependence on acid concentration. In contrast, a single kinetic step with a first‐order dependence with respect to the acid is observed when the experiments are carried out with a deficit of acid. The decrease in the T1 values for the hydride NMR signal of 1 in the presence of added HCl suggests the formation of an adduct with a WH⋅⋅⋅HCl dihydrogen bond. Theoretical calculations for the reaction with HCl indicate that the kinetic results in CH2Cl2 solution can be interpreted on the basis of a mechanism with two competitive pathways. One of the pathways consists of direct proton transfer within the WH⋅⋅⋅HCl adduct to form WCl and H2, whereas the other requires the presence of a second HCl molecule to form a WH⋅⋅⋅HCl⋅⋅⋅HCl adduct that transforms into WCl, H2 and HCl in the rate‐determining step. The activation barriers and the structures of the transition states for both pathways were also calculated, and the results indicate that both pathways can be competitive and that the transition states can be described in both cases as a dihydrogen complex hydrogen‐bonded to Cl− or HCl2−.

2 AbstractDetailed experimental and computational studies are reported on the mechanism of the coupling of alkynes with 3-arylpyrazoles at [Rh(MeCN) suggest that the migratory insertion transition state is close in energy to that for C H bond cleavage. In order to model this result correctly, the DFT calculations must employ the full experimental system and include a treatment of dispersion effects. A significantly higher overall barrier to catalysis is computed at {Ru(p-cymene)} for which the rate-limiting process remains CH activation. However, this is now a one-step process corresponding to the  2 - 1 displacement of acetate, and so is still consistent with the lack of a significant experimental isotope effect (k H /k D = 1.1  0.2).3

The mechanism of the zirconium-catalyzed condensation of carboxylic acids and amines for direct formation of amides was studied using kinetics, NMR spectroscopy, and DFT calculations. The reaction is found to be first order with respect to the catalyst and has a positive rate dependence on amine concentration. A negative rate dependence on carboxylic acid concentration is observed along with S-shaped kinetic profiles under certain conditions, which is consistent with the formation of reversible off-cycle species. Kinetic experiments using reaction progress kinetic analysis protocols demonstrate that inhibition of the catalyst by the amide product can be avoided using a high amine concentration. These insights led to the design of a reaction protocol with improved yields and a decrease in catalyst loading. NMR spectroscopy provides important details of the nature of the zirconium catalyst and serves as the starting point for a theoretical study of the catalytic cycle using DFT calculations. These studies indicate that a dinuclear zirconium species can catalyze the reaction with feasible energy barriers. The amine is proposed to perform a nucleophilic attack at a terminal η-carboxylate ligand of the zirconium catalyst, followed by a C-O bond cleavage step, with an intermediate proton transfer from nitrogen to oxygen facilitated by an additional equivalent of amine. In addition, the DFT calculations reproduce experimentally observed effects on reaction rate, induced by electronically different substituents on the carboxylic acid.