Spin-state changes and reactivity in transition metal chemistry: Reactivity of iron tetracarbonyl

Besora, María; Carreón-Macedo, José-Luis; Cimas, Álvaro; Harvey, Jeremy N.

doi:10.1016/s0898-8838(09)00210-4

Cited by 44 publications

(30 citation statements)

References 145 publications

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“…But as shown in the reaction energy profile, the doublet surface has a lower energy barrier for successful hydrogen liberation. As in many previous cases 42,43,51 this shows that spin crossover can influence the reaction energy profile significantly for successful completion of a chosen reaction pathway. Interestingly, the doublet and the quartet forms of the oxysulfide have similar energies though the latter is calculated to be slightly more stable.…”

Section: Reactivitysupporting

confidence: 73%

Electronic structures and water reactivity of mixed metal sulfide cluster anions

Saha

Raghavachari

2014

The Journal of Chemical Physics

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The electronic structures and chemical reactivity of the mixed metal sulfide cluster anion (MoWS4(-)) have been investigated with density functional theory. Our study reveals the presence of two almost isoenergetic structural isomers, both containing two bridging sulfur atoms in a quartet state. However, the arrangement of the terminal sulfur atoms is different in the two isomers. In one isomer, the two metals are in the same oxidation state (each attached to one terminal S). In the second isomer, the two metals are in different oxidation states (with W in the higher oxidation state attached to both terminal S). The reactivity of water with the two lowest energy isomers has also been studied, with an emphasis on pathways leading to H2 release. The reactive behavior of the two isomers is different though the overall barriers in both systems are small. The origin of the differences are analyzed and discussed. The reaction pathways and barriers are compared with the corresponding behavior of monometallic sulfides (Mo2S4(-) and W2S4(-)) as well as mixed metal oxides (MoWO4(-)).

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Section: Reactivitysupporting

confidence: 73%

Electronic structures and water reactivity of mixed metal sulfide cluster anions

Saha

Raghavachari

2014

The Journal of Chemical Physics

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“…48 It should be noted, however, that there is typically rapid interconversion of spin states for transition metal complexes, faster than microseconds for thermodynamically favored processes. 49 Thus most thermal solution reactions that can access multiple spin states will be under Curtin-Hammett conditions 50 of rapid equilibration of the reactant and product spin states prior to and subsequent to HAT reaction. Under these conditions, reactions will usually proceed over the lowest barrier regardless of spin state.…”

Section: A Broader Viewmentioning

confidence: 99%

Do spin state and spin density affect hydrogen atom transfer reactivity?

2014

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The prevalence of hydrogen atom transfer (HAT) reactions in chemical and biological systems has prompted much interest in establishing and understanding the underlying factors that enable this reactivity. Arguments have been advanced that the electronic spin state of the abstractor and/or the spin-density at the abstracting atom are critical for HAT reactivity. This is consistent with the intuition derived from introductory organic chemistry courses. Herein we present an alternative view on the role of spin state and spin-density in HAT reactions. After a brief introduction, the second section introduces a new and simple fundamental kinetic analysis, which shows that unpaired spin cannot be the dominant effect. The third section examines published computational studies of HAT reactions, which indicates that the spin state affects these reactions indirectly, primarily via changes in driving force. The essay concludes with a broader view of HAT reactivity, including indirect effects of spin and other properties on reactivity. It is suggested that some of the controversy in this area may arise from the diversity of HAT reactions and their overlap with proton-coupled electron transfer (PCET) reactions.

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“…In many cases, DE is quite small. 33 and organometallic systems of interest. However, some large molecular systems and almost all supramolecular and biomolecular systems go well beyond this number of atoms.…”

Section: Theoretical Treatment Of Large Systemsmentioning

confidence: 99%