Trimethylenemethaneiron Tricarbonyl

Emerson, G. F.; Ehrlich, Kenneth C.; Giering, Warren P.; Lauterbur, Paul C.

doi:10.1021/ja00965a077

Cited by 104 publications

(34 citation statements)

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“…One of the four-carbon units complexed to an iron atom is a cisoid 1,3-diene unit leading to a substructure analogous to the known butadiene iron tricarbonyl. However, the other four-carbon unit is a Y-shaped trimethylenemethane unit similar to that found in the known trimethylenemethane-iron tricarbonyl [35,36] The lowest energy structures for the more highly unsaturated binuclear heptalene diiron carbonyl derivatives are higher spin states, namely triplets for C 12 H 10 Fe 2 (CO) n (n ¼ 4, 3) and a quintet for C 12 H 10 Fe 2 (CO) 2 . For C 12 H 10 Fe 2 (CO) n (n ¼ 4, 3) the B3LYP method appears to favor cis structures whereras the BP86 method favors trans structures.…”

Section: Discussionsupporting

confidence: 55%

Binuclear heptalene iron carbonyl complexes: Comparison with related azulene and pentalene complexes

Feng

Sun

et al. 2012

Journal of Organometallic Chemistry

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Section: Discussionsupporting

confidence: 55%

Binuclear heptalene iron carbonyl complexes: Comparison with related azulene and pentalene complexes

Feng

Sun

et al. 2012

Journal of Organometallic Chemistry

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“…The calculated structure ( Figure 5) of the parent methyl-substituted trimethylenemethane (TMM) [24] complex 9 (R ϭ H) reveals the expected coordination mode of the iron fragment to the ligand. This structure is in excellent agreement with X-ray crystal structures of TMMϪFe(CO) 3 derivatives.…”

Section: The Cationic C 5 H 7 ؊Fe(co) 3 Complexesmentioning

confidence: 99%

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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“…5,6 The umbrella-shaped trimethylenemethane ligand, (CH 2 ) 3 C, is another ligand of potential interest in the chemistry of sandwich compounds. Reactions of CH 2 QC(CH 2 Cl) 2 with suitable transition metal derivatives have been used to synthesize the stable iron 7 and chromium 8 carbonyl complexes [(CH 2 ) 3 C]Fe(CO) 3 and [(CH 2 ) 3 C]Cr(CO) 4 , respectively (Fig. 2).…”

Section: Introductionmentioning

confidence: 99%

A new type of sandwich compound: homoleptic bis(trimethylenemethane) complexes of the first row transition metals

et al. 2013

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The metal carbonyl complexes [Z 4 -(CH 2 ) 3 C]Fe(CO) 3 and [Z 4 -(CH 2 ) 3 C]Cr(CO) 4 have been synthesized containing the umbrella-shaped trimethylenemethane ligand. The prospect of using this ligand in the metal sandwich complexes [(CH 2 ) 3 C] 2 M (M = Ti, V, Cr, Mn, Fe, Co, Ni) has now been investigated by density functional theory. The lowest energy structures of such complexes have the metal atom sandwiched between two tetrahapto trimethylenemethane ligands. Singlet spin state structures are strongly preferred for the titanium and nickel derivatives and doublet spin state structures for the vanadium and cobalt derivatives. Similarly, the triplet spin state is preferred for the iron derivative by more than 11 kcal mol À1 . The preferred spin states for the chromium and manganese derivatives depend on the functional used for the structure optimization. Thus the B3LYP and B3LYP* methods predict the higher spin states, namely triplet for chromium and quartet for manganese. However, the BP86 method predicts the lower spin states of singlet for chromium and doublet for manganese. The higher spin state structures for the late transition metal derivatives, namely quintet [(CH 2 ) 3 C] 2 Fe, quartet [(CH 2 ) 3 C] 2 Co, and triplet [(CH 2 ) 3 C] 2 Ni, have trihapto rather than tetrahapto trimethylenemethane ligands. The frontier molecular orbitals in the singlet [(CH 2 ) 3 C] 2 M derivatives (M = Ti, Ni) suggest strong metalligand s and p bonding but insignificant metal-ligand d bonding.

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Trimethylenemethaneiron Tricarbonyl

Cited by 104 publications

References 1 publication

Binuclear heptalene iron carbonyl complexes: Comparison with related azulene and pentalene complexes

Binuclear heptalene iron carbonyl complexes: Comparison with related azulene and pentalene complexes

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

A new type of sandwich compound: homoleptic bis(trimethylenemethane) complexes of the first row transition metals

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