Electron Transfer and Chemical Reactions Associated with the Oxidation of an Extensive Series of Mononuclear Complexes [M(CO)2(κ1-P-P)(κ2-P-P)X] and Binuclear Complexes [{M(CO)2(κ2-P-P)X}2(μ-P-P)] (M = Mn, Re; P-P = Diphosphine or Related Ligand; X = Cl, Br)

Abstract Interaction between light and matter results in new quantum states whose energetics can modify chemical kinetics. In the regime of ensemble vibrational strong coupling (VSC), a macroscopic number $$N$$ N of molecular transitions couple to each resonant cavity mode, yielding two hybrid light–matter (polariton) modes and a reservoir of $$N-1$$ N − 1 dark states whose chemical dynamics are essentially those of the bare molecules. This fact is seemingly in opposition to the recently reported modification of thermally activated ground electronic state reactions under VSC. Here we provide a VSC Marcus–Levich–Jortner electron transfer model that potentially addresses this paradox: although entropy favors the transit through dark-state channels, the chemical kinetics can be dictated by a few polaritonic channels with smaller activation energies. The effects of catalytic VSC are maximal at light–matter resonance, in agreement with experimental observations.

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Zur Elektrochemie von Metall(O)-Verbindungen, V [1] Reaktionen von Diazadien-Metall(VIb)-carbonylkationen und -anionen / Electrochemistry of Metal(O) Compounds, V [1] Reactions of Diazadiene Metal(VIb) Carbonyl Cations and Anions

Zeitschrift für Naturforschung B ◽

10.1515/znb-1982-0312 ◽

1982 ◽

Vol 37 (3) ◽

pp. 324-331 ◽

Cited By ~ 23

Author(s):

Heindirk torn Dieck ◽

Ewald Kühl

Keyword(s):

Electron Transfer ◽

Cyclic Voltammetry ◽

Chemical Reactions ◽

Oxidation States ◽

Transfer Reactions ◽

Carbonyl Complexes ◽

Electron Transfer Reactions ◽

Reactions With Nucleophiles ◽

The Stability ◽

Subsequent Chemical

Abstract Carbonyl complexes of chromium, molybdenum and tungsten of the type DAD M(CO)4 with DAD - diazadiene (R-N=CR′-CR′=NR) are shown by cyclic voltammetry to undergo electron transfer reactions to [DAD M(CO)4]+ and [DAD M(CO)4]-. The rate of subsequent chemical reactions with nucleophiles or by loss of ligands depend on the sol-vent, the metal and the ligands' electronic and steric properties. Chromium(+I) is more readily stabilized than Mo(+I) or W(-I) while the opposite is true for the stability of the anions formed. The dimerisation of a low-coordinate species DAD Mo(CO)3 from the reduction of DAD Mo(CO)3(CH3CN) is detected electrochemically. The stabilization of oxidation states +1 and -I is briefly discussed in view of the DAD ligand properties.

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Molecular Orbital Calculations on the Interaction of PF3 and CO with Ni and Cu Atoms

Zeitschrift für Naturforschung A ◽

10.1515/zna-1982-0407 ◽

1982 ◽

Vol 37 (4) ◽

pp. 346-352 ◽

Cited By ~ 13

Author(s):

H. Itoh ◽

G. Ertl

Keyword(s):

Electron Transfer ◽

Ab Initio ◽

Metal Atom ◽

Electronic Configuration ◽

Orbital Energy ◽

Molecular Orbital Calculations ◽

Mo Calculations ◽

Mononuclear Complexes ◽

Ab Initio Mo Calculations ◽

Adsorption Systems

Abstract The interaction of Ni and Cu atoms with PF3 and CO ligands was investigated by means of ab initio MO calculations. Coupling occurs mainly through the HOMO (8a1 for PF3 and 5 a for CO) levels with the metal 4s and 3dz2 orbitals, if the 3dn-1 4s1 electronic configuration of the metal atom is considered. The estimated M-PF3 bond lengths are 2.0 Å for Ni and 2.5 Å for Cu. Calculations with Ni(3d10) revealed for PF3 a more pronounced electron transfer to the ligand than for CO. The results are consistent with experimental UPS data for mononuclear complexes as well as corresponding adsorption systems. In particular, split-off d-states observed in UPS data for adsorbed PF3 are attributed to the pronounced lowering of the 3d-orbital energy of the metal atom upon interaction with this electropositive ligand.

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