Closely structurally related triplet and quintet iron(IV) oxo complexes with a tetradentate aminopyridine ligand were generated in the gas phase, spectroscopically characterized, and their reactivities in hydrogen-transfer and oxygen-transfer reactions were compared. The spin states were unambiguously assigned based on helium tagging infrared photodissociation (IRPD) spectra of the mass-selected iron complexes. It is shown that the stretching vibrations of the nitrate counterion can be used as a spectral marker of the central iron spin state.

Departament de Quimica and Institute of Computational Chemistry and Catalysis University of Girona Campus Montilivi Girona 17071 Spain

Department of Organic Chemistry Faculty of Science Charles University Prague Hlavova 2030 8 12843 Prague 2 Czech Republic

Serveis Tècnics de Recerca Universitat de Girona Parc Científic i Tecnològic 17003 Girona Spain

Zobrazit více v PubMed

Nam W., Acc. Chem. Res. 2015, 48, 2415–2423. PubMed

Puri M., Que L., Acc. Chem. Res. 2015, 48, 2443–2452. PubMed PMC

Schwarz H., Int. J. Mass Spectrom. 2004, 237, 75–105.

Schröder D., Shaik S., Schwarz H., Acc. Chem. Res. 2000, 33, 139–145. PubMed

Harvey J. N., Poli R., Smith K. M., Coord. Chem. Rev. 2003, 238–239, 347–361.

Shaik S., Hirao H., Kumar D., Acc. Chem. Res. 2007, 40, 532–542. PubMed

Bryliakov K. P., Talsi E. P., Coord. Chem. Rev. 2014, 276, 73–96.

Shaik S., Nat. Chem. 2010, 2, 347–349.

Shaik S., Chen H., Janardanan D., Nat. Chem. 2011, 3, 19–27. PubMed

Janardanan D., Wang Y., Schyman P., L. Que, Jr. , Shaik S., Angew. Chem. Int. Ed. 2010, 49, 3342–3345; PubMed PMC

Angew. Chem. 2010, 122, 3414–3417.

Neu H. M., Quesne M. G., Yang T. S., Prokop-Prigge K. A., Lancaster K. M., Donohoe J., DeBeer S., de Visser S. P., Goldberg D. P., Chem. Eur. J. 2014, 20, 14584–14588. PubMed PMC

Schröder D., Schwarz H., Proc. Natl. Acad. Sci. USA 2008, 105, 18114–18119. PubMed PMC

Donald W. A., McKenzie C. J., O'Hair R. A. J., Angew. Chem. Int. Ed. 2011, 50, 8379–8383; PubMed

Angew. Chem. 2011, 123, 8529–8533.

Schröder D., Schwarz H., Aliaga-Alcalde N., Neese F., Eur. J. Inorg. Chem. 2007, 816–821.

Mas-Ballesté R., McDonald A. R., Reed D., Usharani D., Schyman P., Milko P., Shaik S., L. Que, Jr. , Chem. Eur. J. 2012, 18, 11747–11760. PubMed PMC

Sainna M. A., Kumar S., Kumar D., Fornarini S., Crestoni M. E., de Visser S. P., Chem. Sci. 2015, 6, 1516–1529. PubMed PMC

Company A., Prat I., Frisch J. R., Ballesté R. M., Güell M., Juhász G., Ribas X., Münck E., Luis J. M., L. Que, Jr. , Costas M., Chem. Eur. J. 2011, 17, 1622–1634. PubMed PMC

Schröder D., Roithová J., Schwarz H., Int. J. Mass Spectrom. 2006, 254, 197–201.

Wolk A. B., Leavitt C. M., Garand E., Johnson M. A., Acc. Chem. Res. 2014, 47, 202–210. PubMed

Jašík J., Žabka J., Roithová J., Gerlich D., Int. J. Mass Spectrom. 2013, 354–355, 204–210.

Kelleher P. J., Johnson C. J., Fournier J. A., Johnson M. A., McCoy A. B., J. Phys. Chem. A 2015, 119, 4170–4176. PubMed

Jašík J., Gerlich D., Roithová J., J. Am. Chem. Soc. 2014, 136, 2960–2962. PubMed

Jašík J., Gerlich D., Roithová J., J. Phys. Chem. A 2015, 119, 2532–2542. PubMed

McDonald A. R., L. Que, Jr. , Coord. Chem. Rev. 2013, 257, 414–428.

Hong S., Lee Y.-M., Cho K.-B., Sundaravel K., Cho J., Kim M. J., Shin W., Nam W., J. Am. Chem. Soc. 2011, 133, 11876–11879. PubMed

Wang D., Ray K., Collins M. J., Farquhar E. R., Frisch J. R., Gomez L., Jackson T., Kerscher M., Waleska A., Comba P., Costas M., L. Que, Jr. , Chem. Sci. 2013, 4, 282–291. PubMed PMC

de Visser S. P., Rohde J.-U., Lee Y.-M., Cho J., Nam W., Coord. Chem. Rev. 2013, 257, 381–393.

Armentrout P. B., Int. J. Mass Spectrom. 2000, 200, 219–241.

Schwarz H., Angew. Chem. Int. Ed. 2011, 50, 10096–10115; PubMed

Angew. Chem. 2011, 123, 10276–10297.

Cationic Gold(II) Complexes: Experimental and Theoretical Study

Sulfonyl Nitrene and Amidyl Radical: Structure and Reactivity

Closed Shell Iron(IV) Oxo Complex with an Fe-O Triple Bond: Computational Design, Synthesis, and Reactivity

Chemoselectivity in the Oxidation of Cycloalkenes with a Non-Heme Iron(IV)-Oxo-Chloride Complex: Epoxidation vs. Hydroxylation Selectivity

M-O Bonding Beyond the Oxo Wall: Spectroscopy and Reactivity of Cobalt(III)-Oxyl and Cobalt(III)-Oxo Complexes

Characterized cis-FeV(O)(OH) intermediate mimics enzymatic oxidations in the gas phase