Direct evidence for ligand-enhanced activity of Cu(i) sites.

Little is known about the strong mediating effect of the ligand sphere and the coordination geometry on the strength and isotopologue selectivity of hydrogen adsorption on the undercoordinated copper(i) site. Here, we explore this effect using gas-phase complexes Cu(HO)(H) (with ≤ 3) as model systems. Cu(HO) attracts dihydrogen (82 kJ mol ) more strongly than bare Cu (64 kJ mol ) does.

Visible-Light-Triggered Photoswitching of Diphosphene Complexes.

Although diphosphene transition metal complexes are known to undergo E to Z isomerization upon irradiation with UV light, their potential for photoswitching has remained poorly explored. In this study, we present diphosphene complexes capable of reversible photoisomerizations through haptotropic rearrangements. The compounds [(2-κ P,κ C)Mo(CO) ][OTf] (3 a[OTf]), [(2-κ P,κ C)Fe(CO)][OTf] (3 b[OTf]), and [(2-κ P)Fe(CO) ][OTf] (4[OTf]) were prepared using the triflate salt [(L )P=P(Dipp)][OTf] (2[OTf) as a precursor (L =4,5-dichloro-1,3-bis(2,6-diisiopropylphenyl)-imidazolin-2-yl; Dipp=2,6-diisiopropylphenyl, OTf=triflate).

Chemical bonding of HF, HCl, and H O onto YF surfaces: Quantification by first principles.

The surfaces of waimirite β- have been studied for their fluorine and chlorine versus water affinity. Bonding patterns of HF, HCl, and chemically adsorbed onto surfaces of (010), (100), (011), and (101) have been quantified by density functional theory applying energy decomposition analysis. We found that the adsorption of is dominated by about 65% of electrostatics, which causes a low surface sensitivity and weak interactions.

Surface functionalization with nonalternant aromatic compounds: a computational study of azulene and naphthalene on Si(001).

Nonalternant aromatic π-electron systems show promises for surface functionalization due to their unusual electronic structure. Based on our previous experiences for metal surfaces, we investigate the adsorption structures, adsorption dynamics and bonding characteristics of azulene and its alternant aromatic isomer naphthalene on the Si(001) surface. Using a combination of density functional theory,molecular dynamics, reaction path sampling and bonding analysis with the energy decomposition analysis for extended systems, we show that azulene shows direct adsorption paths into several, strongly bonded chemisorbed final structures with up to four covalent carbon-silicon bonds which can be described in a donor-acceptor and a shared-electron bonding picture nearly equivalently.