Intramolecular environmental effects on the bonding in transition metal-pentacyanonitrosyl complexes

Principles of structure, bonding, and reactivity for metal nitrosyl complexes

The seminal discovery of light-induced changes in transition-metal nitrosyl complexes in the late 1970s and their identification as metastable linkage isomers almost 20 years after the initial discoveries have in recent years motivated a plethora of experimental and theoretical studies. They have raised the question of whether the linkage isomers play a role in the many crucial biological processes involving nitric oxide, which though likely, is still a subject of investigation. The linkage isomers have potential technological importance, as the change in refractive index on a molecular scale, associated with the photoinduced change in the crystals, in principle allows the design of very high capacity storage devices. This review summarizes the current knowledge in the still-developing field and includes a discussion of photoinduced metastable linkage isomers of related substances.

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Photoinduced linkage isomers of transition-metal nitrosyl compounds and related complexes.

Distinct spectral features at the Fe L-edge of the two compounds K3[Fe(CN)6] and K4[Fe(CN)6] have been identified and characterized as arising from contributions of the ligand π* orbitals due to metal-to-ligand back-bonding. In addition, the L-edge energy shifts and total intensities allow changes in the ligand field and effective nuclear charge to be determined. It is found that the ligand field term dominates the edge energy shift. The results of the experimental analysis were compared to BP86 DFT calculations. The overall agreement between the calculations and experiment is good; however, a larger difference in the amount of π back-donation between Fe(II) and Fe(III) is found experimentally. The analysis of L-edge spectral shape, energy shift, and total intensity demonstrates that Fe L-edge X-ray absorption spectroscopy provides a direct probe of metal-to-ligand back-bonding.

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Intramolecular environmental effects on the bonding in transition metal-pentacyanonitrosyl complexes

Citations

Principles of structure, bonding, and reactivity for metal nitrosyl complexes

Photoinduced linkage isomers of transition-metal nitrosyl compounds and related complexes.

Fe L-Edge XAS Studies of K4[Fe(CN)6] and K3[Fe(CN)6]: A Direct Probe of Back-Bonding

New features in the redox coordination chemistry of metal nitrosyls {M-NO+ ; M-NO•; M-NO- (HNO)}

Nitrosyl complexes of ruthenium

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