The Structure of [Fe(CO)4]—An Important New Chapter in a Long-Running Story

Poliakoff, Martyn; Turner, James J.

doi:10.1002/1521-3773(20010803)40:15<2809::aid-anie2809>3.0.co;2-u

Cited by 70 publications

(64 citation statements)

References 27 publications

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“…Another possibility is that this absorption is to a relatively long-lived excited triplet state of VC [18]. Excited triplet states of the coordinatively unsaturated complexes CpCo(CO) [19] and Fe(CO) 4 [20] do not appear to solvate, and the IR spectrum of solvated singlet Fe(CO) 4 has C Á/O stretches that are coincident or near-coincident with those of the unsolvated triplet [20].…”

Section: Resultsmentioning

confidence: 99%

Unusual behavior in the 308 nm flash photolysis of Vaska's complex

Schultz

2003

Journal of Organometallic Chemistry

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Section: Resultsmentioning

confidence: 99%

Unusual behavior in the 308 nm flash photolysis of Vaska's complex

Schultz

2003

Journal of Organometallic Chemistry

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“…Furthermore, the Fe center is sterically free to interact with the solvent, making it a strong electrophile. The question thus arises whether the reactivity of Fe(CO) 4 towards solution modifies the exited-state relaxation pathways 42 . As reported in our earlier publication, 1 we concluded that after photodissociation of Fe(CO) 5 , the reactive species Fe(CO) 4 converts from an excited singlet state to the triplet ground state and, in a parallel pathway, combines with an ethanol solvent molecule to form Fe(CO) 4 EtOH or geminately with CO to reform Fe(CO) 5 on a time scale of 200–300 fs.…”

Section: Introductionmentioning

confidence: 99%

“…While singlet Fe(CO) 4 is highly reactive, the 3 B 2 electronic ground state of Fe(CO) 4 does not coordinate with solvent 42 . The occurrence of 3 B 2 Fe(CO) 4 is established in several solutions, but the mechanistic details of its creation had remained unresolved 35,36,40,42 .…”

Section: Introductionmentioning

confidence: 99%

Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH

Kunnus

Josefsson

Rajković

et al. 2016

Structural Dynamics

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We utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO)5 in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)4 which are observed following a charge transfer photoexcitation of Fe(CO)5 as reported in our previous study [Wernet et al., Nature 520, 78 (2015)]. We find that branching of the reaction pathway likely happens in the 1A1 state of Fe(CO)4. A sub-picosecond time constant of the spin crossover from 1B2 to 3B2 is rationalized by the proposed 1B2 → 1A1 → 3B2 mechanism. Ultrafast ligation of the 1B2 Fe(CO)4 state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the 3B2 Fe(CO)4 ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via 1B2 → 1A1 → 1A′ Fe(CO)4EtOH pathway and the time scale of the 1A1 Fe(CO)4 state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.

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“…We address photo-dissociation of the prototypical transition-metal carbonyl molecule Fe(CO)5 both in the gas phase and in solution ( Figure 1) [1]. How chemical bonding evolves during these reactions is largely unknown and the reaction pathway is debated in solution [2][3][4].…”

Section: Introductionmentioning

confidence: 99%