The Sabatier activity volcano provides intuitive guide for catalyst design, but also imposes fundamental limitations on the composition and maximal of catalysts. We show that ORR is shifted reshaped by potential-dependent fluxionality subnano cluster Fluxionality causes typically under-binding Ag/Au to gain optimal in form, surpass Pt/Pd. Furthermore, isomerization clusters as a function potent...

Monometallic complexes of the tetrakis(pyrazolyl)borate ligand [ML(2){B(pz)(4)}] {M = Rh, Ir; L(2) = eta-cod, eta-nbd, (CO)(2), (CO)(PPh(3))} have two free pyrazolyl rings which can be coordinated to a second ML(2) unit to give the dimeric compounds [L(2)M{mu-B(pz)(4)}ML(2)](+), and to a metal halide to give heterobimetallic species [L(2)M{mu-B(pz)(4)}M'Cl(2)]. (1)H NMR spectroscopy shows that ...

Pd(II) complexes in which 2-pyridyldiphenylphosphine (Ph(2)Ppy) chelates the Pd(II) centre have been prepared and characterized by multinuclear NMR spectroscopy and by X-ray crystallographic analysis. trans-[Pd(kappa(1)-Ph(2)Ppy)(2)Cl(2)] is transformed into [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)Cl]Cl by the addition of a few drops of methanol to dichloromethane solutions, and into [Pd(kappa...

The synthesis and structural and spectroscopic characterization of a family of copper(I) complexes, containing a dinucleating hexaaza macrocyclic ligand, of general formula [Cu(2)(L)(X)(2)](2+) (L = Me2p, Me2m, Me3p, or Me3m; X = MeCN, n-PrCN, CO, t-BuNC, or PPh(3)) is described. This family of complexes contains ligands that differ from one another in the number of methylenic units linking the...

The dinuclear Pt-Au complex [(CNC)(PPh3)PtAu(PPh3)](ClO4) (2) (CNC = 2,6-diphenylpyridinate) has been prepared. Its crystal structure shows a rare metal-metal bonding situation, with very short Pt–Au and Au-Cipso(CNC) distances and dissimilar Pt-Cipso(CNC) bonds. Multinuclear NMR spectra of 2 show the persistence of the Pt–Au bond in solution and the operation of an unusual fluxional behavior i...

In this article, the complexes [Rh(Binor-S )(PR3)][BAr4] (R iPr, Cy, C5H9) are described. A combination of x-ray crystallography, NMR spectroscopy, density functional theory, and ‘‘atoms in molecules’’ calculations unequivocally demonstrates that the complexes contain rare examples of metal C–C agostic interactions. Moreover, they are fluxional on the NMR time scale, undergoing rapid and revers...

The dynamics of iron tetracarbonyl olefin complexes has been investigated using two-dimensional infrared (2D-IR) spectroscopy. Cross peaks between all CO-stretching bands show that the CO-stretch modes are coupled, and from the cross-peak anisotropies we can confirm previous assignments of the absorption bands. From the pump-probe delay dependence of the diagonal peaks in the 2D-IR spectrum we ...