Structure and Fluxional Behavior of (η4-butadiene)Fe(CO)2L (L = CO, PH3, PMe3) Complexes. A Density Functional Study

González-Blanco, Òscar; Branchadell, V.

doi:10.1021/om960896+

Cited by 18 publications

(15 citation statements)

References 46 publications

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“…Carbon ± carbon distances in the butadiene moiety of the diene show the same trends upon complexation that have already been reported for 1 [10] and show only slight variations upon substitution on C 4 . Finally, the comparison between the s-cis and s-trans conformers for each complex does not show any significant difference.…”

Section: Resultssupporting

confidence: 85%

“…[10±12] The gas-phase structure [13,14] and the vibrational spectra [15±17] are well reproduced by density functional calculations. [10] Moreover, the computed conformational barrier [10] corresponding to the turnstile rotation [18] of the butadiene ligand relative to the Fe(CO) 3 moiety is in excellent agreement with experiment. [19±24] The organoiron complexes studied here have p systems vicinal to the organometallic unit and they can be separated in two groups: the derivatives substituted with a carbonyl group (aldehyde or ketone), 2, and the olefinic systems, 5.…”

Section: Introductionsupporting

confidence: 63%

“…For Fe(CO) 3 the preparation term was computed from the 3 A 2 ground state of a C 3v structure, [56,57] while in the complex we have considered it to exist in a singlet state. [10] For the butadiene fragments we have considered the distortion from their minimum energy conformation, that is, an s-trans arrangement for the C 1 À C 2 À C 3 À C 4 moiety to the s-cis arrangement in the complex. E st is the steric interaction term.…”

Section: Fragment Can Be Formulated [Eq (1)] In Whichmentioning

confidence: 99%

“…[10] The decomposition of this term shows a bond that is clearly dominated by the backdonation interaction. The presence of the electron-withdrawing carbonylic group in 2 a and 2 b makes the diene a stronger acceptor, thus enhancing the back-donation from the metal to the diene with respect to that of 1.…”

Section: Fragment Can Be Formulated [Eq (1)] In Whichmentioning

confidence: 99%

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Structure and Conformational Equilibrium in Substituted [(η4-butadiene)Fe(CO)3] Complexes: A Density Functional Study

1999

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The energy profiles corresponding to CÀC rotation in several carbonyland olefin-substituted derivatives of [(h 4 -butadiene)Fe(CO) 3 ] have been studied through density functional calculations. The energy differences between s-cis and s-trans conformations show an excellent correlation with the diastereoselectivities experimentally observed in several reactions. These energy differences have been rationalized through an analysis of the iron ± butadiene bond, and the role played by the metal in the conformational preferences is discussed.Keywords: asymmetric synthesisć onformation analysis´density functional calculations´iron´nucleophilic additions [b] Dr. R

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Section: Resultssupporting

confidence: 85%

Section: Introductionsupporting

confidence: 63%

Section: Fragment Can Be Formulated [Eq (1)] In Whichmentioning

confidence: 99%

Section: Fragment Can Be Formulated [Eq (1)] In Whichmentioning

confidence: 99%

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Structure and Conformational Equilibrium in Substituted [(η4-butadiene)Fe(CO)3] Complexes: A Density Functional Study

1999

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“…The symmetry is not crystallographically imposed; as it is also present in the gas phase species, as shown by microwave spectroscopy [33]. The bonding present in the complex has been discussed previously [34].…”

Section: Resultsmentioning

confidence: 96%

Vibrational spectra of buta-1,3-diene iron tricarbonyl: comparison to surface species

Parker

Carias

Tomkinson

2017

Catalysis, Structure & Reactivity

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angle of ~30°. Both the s-cis and the gauche conformers are high energy states, ~15 kJ mol −1 above the ground state and also well above the 2.5 kJ mol −1 corresponding to 300 K. Thus the gauche conformer has only been detected in the gas phase [3] at high temperature or by matrix isolation of the high temperature vapour [4, 5]. However, it is possible to stabilise the s-cis conformer by complexation and the compound [6] C 4 H 6 Fe(CO) 3 (see Figure 2) is an example of this. The vibrational spectroscopy of butadiene has been extensively studied both as the free molecule e.g. [4, 5, 7] and adsorbed on a variety of oxide [8, 9] and metal surfaces [10-16]. Butadiene potentially exhibits many different modes of bonding to a surface [17], the aim of this work is to fully characterise how the spectrum of the s-cis conformer changes on coordination. Stateof-the art computational methods enable transition

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Structural and Energetical Characterization of the Methylbutadiene–Fe(CO)3 Isomers and Related Reactive Intermediates with Quantum Chemical Methods

Pfletschinger

Schmalz²,

Koch³

1999

Eur. J. Inorg. Chem.

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A theoretical investigation of isoprene–Fe(CO)3 (2), (E)‐1,3‐pentadiene–Fe(CO)3 (3), (Z)‐1,3‐pentadiene–Fe(CO)3 (4), and reactive intermediates derived from these complexes was undertaken, employing the HF/DFT hybrid functional Becke3LYP, and the results are presented. Special emphasis is placed on cationic, anionic, and radical intermediates formally derived by abstraction of a hydride, a proton, or a hydrogen atom from the methyl group of the parent complexes. The geometry, energy, and electronic situation of the calculated species are discussed in the context of experimental facts. This leads to a better mechanistic understanding of the chemistry of acyclic butadiene–Fe(CO)3 complexes, provides insights into structural details of the intermediates involved, and allows the evaluation of possible resonance formulae. The calculation of transition states of isomerization (or racemization) processes even permits a quantitative description of energy profiles. In this way, the configurational stability of relevant cationic, anionic and radical intermediates can be estimated.

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Structure and Fluxional Behavior of (η⁴-butadiene)Fe(CO)₂L (L = CO, PH₃, PMe₃) Complexes. A Density Functional Study

Cited by 18 publications

References 46 publications

Structure and Conformational Equilibrium in Substituted [(η4-butadiene)Fe(CO)3] Complexes: A Density Functional Study

Structure and Conformational Equilibrium in Substituted [(η4-butadiene)Fe(CO)3] Complexes: A Density Functional Study

Vibrational spectra of buta-1,3-diene iron tricarbonyl: comparison to surface species

Structural and Energetical Characterization of the Methylbutadiene–Fe(CO)3 Isomers and Related Reactive Intermediates with Quantum Chemical Methods

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