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A Ce atom reaction with propene is carried out in a pulsed laser vaporization molecule beam source. Several Ce–hydrocarbon species formed by the C—H and C—C bond activation of propene are observed by time-of-flight mass spectrometry, and Ce(C3Hn) (n = 4 and 6) are characterized by mass-analyzed threshold ionization (MATI) spectroscopy and density functional theory, multiconfiguration, and relativistic quantum chemical calculations. The MATI spectrum of each species consists of two vibronic band systems, each with several vibronic bands. Ce(C3H6) is identified as an inserted species with Ce inserting into an allylic C—H bond of propene and Ce(C3H4) as a metallocycle through 1,2-vinylic dehydrogenation. Both species have a Cs structure with the Ce 4f16s1 ground valence electron configuration in the neutral molecule and the Ce 4f1 configuration in the singly charged ion. The two vibronic band systems observed for each species are attributed to the ionization of two pairs of the lowest spin–orbit coupled states with each pair being nearly degenerate. [ABSTRACT FROM AUTHOR]

Metal-mediated N–H and C–H bond activation of aliphatic amines is an effective strategy for synthesizing biologically important molecules. Ln (Ln = La and Ce) atom reactions with dimethylamine are carried out in a pulsed-laser vaporization supersonic molecular beam source. A series of dehydrogenation species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln-containing species in the formula Ln(CH2NCH3) are characterized by single-photon mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and multiconfiguration self-consistent field and quasi-degenerate perturbation theory for the Ce species. The MATI spectrum of La(CH2NCH3) consists of a single vibronic band system, which is assigned to the ionization of the doublet ground state of N-methyl-lanthanaaziridine. The MATI spectrum of Ce(CH2NCH3) displays two vibronic band systems, which are attributed to the ionization of two-pair lowest-energy spin–orbit coupling states of N-methyl-ceraaziridine. Both metallaaziridines are three-membered metallacycles and formed by the thermodynamically and kinetically favorable concerted dehydrogenation of the amino group and one of the methyl groups. [ABSTRACT FROM AUTHOR]

Ln (Ln = La and Ce) atom reactions with methylamine are carried out in a pulsed-laser vaporization supersonic molecular beam source. A series of dehydrogenation species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln-containing species in the formula Ln(NCH3) are characterized by mass-analyzed threshold ionization (MATI) spectroscopy and density functional theory and multiconfiguration spin–orbit coupling computations. The MATI spectrum of La(NCH3) consists of two vibronic band systems that are assigned to the ionization of the 2A1 ground state of the C3v isomer La(N–CH3) and the 2A′ ground state of the Cs isomer La(NH–CH2). The MATI spectrum of Ce(NCH3) also displays two band systems, which are attributed to the ionization of the low-energy spin–orbit coupling states of the C3v isomer Ce(N–CH3). Ln(N–CH3) is formed by the concerted dehydrogenation of the amino group, while La(NH–CH2) is formed by the dehydrogenation of both amino and methyl groups. Ce(NH–CH2) is presumably formed in the reaction based on the computational predictions but not observed by the spectroscopic measurements. [ABSTRACT FROM AUTHOR]

Ce atom reactions with ethylene, 2-butene, and isobutene are carried out in a pulsed laser vaporization molecule beam source. Ce-containing species are observed with time-of-flight mass spectrometry, and Ce(C4H6) is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and relativistic quantum chemical calculations. Two structural isomers are identified for Ce(C4H6): one is the tetrahedronlike Ce[C(CH2)3] in C3v symmetry and the other is the five-membered metallocyclic Ce(CH2CHCHCH2) in Cs. The MATI spectrum of the C3v isomer exhibits two vibronic band systems separated by 88 cm−1, while that of the Cs isomer displays three split by 60 and 101 cm−1. The multiple band systems are attributed to spin-orbit splitting and vibronic transitions involving metal-hydrocarbon and hydrocarbon-based vibrations. The splitting in the C3v isomer arises from interactions of two triplet and two singlet states at the lowest energies, while each splitting in the Cs isomer involves two triplets and a singlet. Although the Ce atom has ground electron configuration 4f15d16s2, Ce valence electron configurations in both isomers are 4f16s1 in the neutral ground state and 4f1 in the ion. The remaining Ce 5d electrons in the isolated atom are spin paired in molecular orbitals that are a bonding combination between Ce 5dπ and hydrocarbon π* orbitals. [ABSTRACT FROM AUTHOR]

Group 3 metal-aniline complexes, M(aniline) (M = Sc, Y, and La), are produced in a pulsed laser-vaporization molecular beam source, identified by photoionization time-of-flight mass spectrometry, and investigated by pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy and quantum chemical calculations. Adiabatic ionization energies and several low-frequency vibrational modes are measured for the first time from the ZEKE spectra. Metal binding sites and electronic states are determined by combining the ZEKE measurements with the theoretical calculations. The ionization energies of the complexes decrease down the metal group. An out-of-plane ring deformation mode coupled with an asymmetric metal-carbon stretch is considerably anharmonic. Although aniline has various possible sites for metal coordination, the preferred site is the phenyl ring. The metal binding with the phenyl ring yields syn and anti conformers with the metal atom and amino hydrogens on the same and opposite sides of the ring, respectively. The anti conformer is determined to be the spectral carrier. The ground electronic state of the anti conformer of each neutral complex is a doublet with a metal-based electron configuration of nd2(n + 1)s1, and the ground electronic state of each ion is a singlet with a metal-based electron configuration of nd2. The formation of the neutral complexes requires the nd2(n + 1)s1 ← nd1(n + 1)s2 electron excitation in the metal atoms. [ABSTRACT FROM AUTHOR]