The first catalytic and enantioselective C-H direct acylation of ferrocene derivatives has been developed. A series of 2-acyl-1-dimethylaminomethylferrocenes with planar chirality were provided under highly efficient and concise one-pot conditions with up to 85% yield and 98% ee. The products obtained could be easily converted to various chiral ligands via diverse transformations.

We have developed an integrated instrument combining deep ultraviolet laser ionization mass spectrometry (DUV-LIMS) and infrared multiphoton dissociation (IR-MPD) spectroscopy, abbreviated as DUV-IR. The 177.3 nm DUV laser (7 eV single-photon energy) has short pulse duration (15 ps) and appropriate pulse energy (∼20 µJ), which is found to be highly efficient for low-fragment photoionization of neutral metal clusters and molecules. A home-made cluster source is designed with an adjustable formation channel suitable for the generation of different cluster series. The well-aligned components of the reflection time-of-flight mass spectrometer, as well as the coaxial design of DUV laser and molecular beam, bring forth high sensitivity and high resolution of the DUV-LIMS. Taking these advantages, well-resolved neutral Vn (n = 1–43) and (Benzene)n (n = 1–25) clusters have been generated free of fragmentation. In addition to the generation and detection of neutral clusters, a fast-flow reaction tube is also designed downstream of the cluster source allowing to study their reactivity. In particular, a broad-range tunable IR laser (1.3–16 µm) is coupled with the DUV laser to attain IR-MPD spectroscopic analysis. This integrated system offers a general protocol to prepare various clusters to study their gas-phase reactivity and to determine their structures.

Water and its interactions with metals are closely bound up with human life, and the reactivity of metal clusters with water is of fundamental importance for the understanding of hydrogen generation. Here a prominent hydrogen evolution reaction (HER) of single water molecule on vanadium clusters Vn+ (3 ≤ n ≤ 30) is observed in the reaction of cationic vanadium clusters with water at room temperature. The combined experimental and theoretical studies reveal that the wagging vibrations of a V-OH group give rise to readily formed V-O-V intermediate states on Vn+ (n ≥ 3) clusters and allow the terminal hydrogen to interact with an adsorbed hydrogen atom, enabling hydrogen release. The presence of three metal atoms reduces the energy barrier of the rate-determining step, giving rise to an effective production of hydrogen from single water molecules. This mechanism differs from dissociative chemisorption of multiple water molecules on aluminium cluster anions, which usually proceeds by dissociative chemisorption of at least two water molecules at multiple surface sites followed by a recombination of the adsorbed hydrogen atoms.