High‐Spin and Low‐Spin State Perferryl Intermediates: Reactivity‐Selectivity Correlation in Fe(PDP) Catalyzed Oxidation of (+)‐Sclareolide

AbstractUsing the Unrestricted Hartree-Fock method and supercells containing up to 160 atoms, we calculated the energy level positions in the gap and atomic geometry for the Fe4+ impurity substituting for a host Ti atom in SrTiO3. In agreement with experiment, the high spin (S=2) state is much lower in energy than the zero-spin state. The energy level positions strongly depend on the asymmetric displacement mode of the six nearest O ions which is a combination of the Jahn-Teller and breathing modes. A considerable covalent bonding between the Fe ion and four nearest O ions takes place.

Download Full-text

On the Role of the High-Spin State in the Water Exchange Reaction of Hexaaquocobalt(III)

Comments on Inorganic Chemistry ◽

10.1080/02603598108078079 ◽

1981 ◽

Vol 1 (1) ◽

pp. 47-51 ◽

Cited By ~ 11

Author(s):

Jay R. Winkler ◽

Steven F. Rice ◽

Harry B. Gray

Keyword(s):

Exchange Reaction ◽

High Spin ◽

Spin State ◽

Water Exchange ◽

High Spin State

Download Full-text

Electric Field Induced Room Temperature Null to High Spin State Switching: A Computational Prediction

Advanced Theory and Simulations ◽

10.1002/adts.201900005 ◽

2019 ◽

Vol 2 (4) ◽

pp. 1900005 ◽

Cited By ~ 1

Author(s):

Carlos O. Amorim ◽

João S. Amaral ◽

João N. Gonçalves ◽

Vítor S. Amaral

Keyword(s):

Electric Field ◽

High Spin ◽

Spin State ◽

Room Temperature ◽

High Spin State ◽

Computational Prediction ◽

State Switching

Download Full-text

Vibrational Coherences and Relaxation in the High-Spin State of Aqueous [FeII(bpy)3]2+

Angewandte Chemie ◽

10.1002/ange.200902728 ◽

2009 ◽

Vol 121 (39) ◽

pp. 7320-7323 ◽

Cited By ~ 24

Author(s):

Cristina Consani ◽

Mirabelle Prémont-Schwarz ◽

Amal ElNahhas ◽

Christian Bressler ◽

Frank van Mourik ◽

...

Keyword(s):

High Spin ◽

Spin State ◽

High Spin State

Download Full-text

Ionic complex of fullerene C602− dianions with (MDABCO+)2·MnIITPP coordination assemblies: synthesis, crystal structure and magnetic properties

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424608000510 ◽

2008 ◽

Vol 12 (11) ◽

pp. 1146-1153 ◽

Cited By ~ 10

Author(s):

Dmitri V. Konarev ◽

Salavat S. Khasanov ◽

Gunzi Saito ◽

Rimma N. Lyubovskaya

Keyword(s):

High Spin ◽

Spin State ◽

Magnetic Measurements ◽

High Spin State ◽

Radial Expansion ◽

Ionic Complex ◽

Porphyrin Core ◽

First Time ◽

Center Distance ◽

Positively Charged

The crystals of the ionic complex containing fullerene C 602− dianions and positively charged ( MDABCO +)2· Mn II TPP assemblies: {( MDABCO +)2·MnII TPP }·( C 602−)·( C 6 H 4 Cl 2)4·( CH 3 CN )2 (1) were obtained for the first time ( MDABCO +: the cation of N-methyldiazabicyclooctane; TPP: tetraphenylporphyrin). The C 602− dianions are isolated in the complex with the shortest center-to-center distance of 13.228 Å. The Mn II atoms are six-coordinated in the ( MDABCO +)2· Mn II TPP units. The length of the Mn-N(TPP) equatorial bonds of 2.093-2.098(1) Å corresponds to the high-spin state of the Mn II atoms (S = 5/2) which was confirmed by the magnetic measurements (µ eff = 5.61 µ B at 300 K). The Mn II atoms are located exactly in the porphyrin plane and this results in the radial expansion of the porphyrin core. The long (2.537(1)−2.545(1) Å) Mn - N ( MDABCO +) axial bonds indicate essential destabilization of the six-coordinated ( MDABCO +)2· Mn II TPP units due to the population of the d ( z 2) orbital in high-spin state. The contribution from the C 602− dianions was not found in magnetic measurements on the basis of the contribution from high-spin Mn II TPP and most probably they are diamagnetic in the 2-300 K range.

Download Full-text