Metal−Phosphorus Bonding in Fe(CO)<sub>4</sub>PR<sub>3</sub> Complexes. A Density Functional Study

González-Blanco, Òscar; Branchadell, V.

doi:10.1021/om9705214

Cited by 61 publications

(53 citation statements)

References 70 publications

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“…Experimental evidence and qualitative molecular orbital considerations suggest that strong p-accepting ligands prefer the equatorial position of trigonal bipyramidal complexes containing d 8 number of quantum chemical studies of complexes Fe(CO) 4 L (L = N 2 [18], H 2 [19], PR 3 [20], C 2 H 4 [21] and C 2 H 2 [22]). Experimental evidence and qualitative molecular orbital considerations suggest that strong p-accepting ligands prefer the equatorial position of trigonal bipyramidal complexes containing d 8 number of quantum chemical studies of complexes Fe(CO) 4 L (L = N 2 [18], H 2 [19], PR 3 [20], C 2 H 4 [21] and C 2 H 2 [22]).…”

Section: Introductionmentioning

confidence: 99%

“…Experimental evidence and qualitative molecular orbital considerations suggest that strong p-accepting ligands prefer the equatorial position of trigonal bipyramidal complexes containing d 8 metals, while r-donor ligands prefer axial coordination sites [16±17]. This model was studied by a limited number of quantum chemical studies of complexes Fe(CO) 4 L (L = N 2 [18], H 2 [19], PR 3 [20], C 2 H 4 [21] and C 2 H 2 [22]). However, no systematic and comparative theoretical work with respect to a wider range of such complexes has been published so far.…”

Section: Introductionmentioning

confidence: 99%

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Ligand Site Preference in Iron Tetracarbonyl Complexes Fe(CO) ₄ L (L = CO, CS, N ₂ , NO ⁺ , CN ^– , NC ^– , η ² ‐C ₂ H ₄ , η ² ‐C ₂ H ₂

Chen

Hartmann

Frenking

2001

Z. anorg. allg. Chem.

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Equilibrium geometries, bond dissociation energies and relative energies of axial and equatorial iron tetracarbonyl complexes of the general type Fe(CO) 4 L (L = CO, CS, N2, NO + , CN ± , NC ± , g 2 -C 2 H 4 , g 2 -C 2 H 2 , CCH 2 , CH 2 , CF 2 , NH 3 , NF 3 , PH 3 , PF 3 , g 2 -H 2 ) are calculated in order to investigate whether or not the ligand site preference of these ligands correlates with the ratio of their r-donor/p-acceptor capabilities. Using density functional theory and effectivecore potentials with a valence basis set of DZP quality for iron and a 6-31G(d) all-electron basis set for the other elements gives theoretically predicted structural parameters that are in very good agreement with previous results and available experimental data. Improved estimates for the (CO) 4 Fe±L bond dissociation energies (D 0 ) are obtained using the CCSD(T)/II//B3LYP/II combination of theoretical methods. The strongest Fe±L bonds are found for complexes involving NO + , CN ± , CH 2 and CCH 2 with bond dissociation energies of 105.1, 96.5, 87.4 and 83.8 kcal mol ±1 , respectively. These values decrease to 78.6, 64.3 and 64.2 kcal mol ±1 , respectively, for NC ± , CF 2 and CS. The Fe(CO) 4 L complexes with L = CO, g 2 -C 2 H 4 , g 2 -C 2 H 2 , NH 3 , PH 3 and PF 3 have even smaller bond dissociation energies ranging from 45.2 to 37.3 kcal mol ±1 . Finally, the smallest bond dissociation energies of 23.5, 22.9 and 18.5 kcal mol ±1 , respectively are found for the ligands NF 3 , N 2 and g 2 -H 2 . A detailed examination of the (CO) 4 Fe±L bond in terms of a semi-quantitative Dewar-Chatt-Duncanson (DCD) model is presented on the basis of the CDA and NBO approach. The comparison of the relative energies between axial and equatorial isomers of the various Fe(CO) 4 L complexes with the r-donor/p-acceptor ratio of their respective ligands L thus does not generally support the classical picture of p-accepting ligands preferring equatorial coordination sites and r-donors tending to coordinate in axial positions. In particular, this is shown by iron tetracarbonyl complexes with L = g 2 -C 2 H 2 , g 2 -C 2 H 4 , g 2 -H 2 . Although these ligands are predicted by the CDA to be stronger r-donors than p-acceptors, the equatorial isomers of these complexes are more stable than their axial pendants.

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Section: Introductionmentioning

confidence: 99%

“…Experimental evidence and qualitative molecular orbital considerations suggest that strong p-accepting ligands prefer the equatorial position of trigonal bipyramidal complexes containing d 8 metals, while r-donor ligands prefer axial coordination sites [16±17]. This model was studied by a limited number of quantum chemical studies of complexes Fe(CO) 4 L (L = N 2 [18], H 2 [19], PR 3 [20], C 2 H 4 [21] and C 2 H 2 [22]). However, no systematic and comparative theoretical work with respect to a wider range of such complexes has been published so far.…”

Section: Introductionmentioning

confidence: 99%

Ligand Site Preference in Iron Tetracarbonyl Complexes Fe(CO) ₄ L (L = CO, CS, N ₂ , NO ⁺ , CN ^– , NC ^– , η ² ‐C ₂ H ₄ , η ² ‐C ₂ H ₂

Chen

Hartmann

Frenking

2001

Z. anorg. allg. Chem.

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“…Recently, Schmid et al [16] and González-Blanco and Branchadell [17] have shown that PH 3 cannot model the PPh 3 when processes that involve the cleavage or formation of M-P bonds are involved. Gleich et al [18] used a combined quantum mechanical/molecular mechanical (QM/MM) approach to determine the regioselectivities in the rhodium-catalyzed hydroformylation of propene.…”

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confidence: 99%

Insertion reaction of propene into Rh?H bond in HRh(CO)(PH3)2(C3H6) compound: A density functional study

Rocha

Almeida

2000

Int. J. Quant. Chem.

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ABSTRACT:Quantum mechanical calculations at the MP4 (SDQ) level using the BP86-optimized geometries were carried out to investigate the energies and reaction mechanism for the propene (CH 3 -C 1 H=CH 2 2 ) insertion reaction into the Rh-H bond, using the cis-HRh(CO)(PH 3 ) 2 compound as a model catalytic species. Since the reaction may occur on the branched carbon 1 or in the normal carbon 2, which leads to branched and normal Rh(alkyl) compounds, respectively, we investigated these two mechanisms. The results show that the insertion in the branched carbon has an activation energy of 16.2 kcal/mol, and the activation energy for the reaction to take place at the normal carbon is 14.3 kcal/mol. These activation energies, together with the calculated relative energy of the metal-alkyl compounds formed after the insertion considering these two pathways, were used to access the regioselectivity on this reaction. We found a ratio of normal-and iso-products, n:iso, of (96:4), which is in excellent agreement with the experimental regioselectity of (95:5).

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“…19 While electron acceptor ability of a molecule is related with E LUMO , E HOMO represents σ -donor ability. 31,32 When we move from O to Se, the energy of LUMO decreases and that of HOMO increases. The energies of HOMO and LUMO for the compounds 2-4 indicate that the relative order of σ -donation is 4 > 3 > 2.…”

Section: Theoretical Calculationsmentioning

confidence: 99%

Synthesis, Characterization and Ab Initio Calculations of Aminophosphine Derived From 4-Benzylpiperidine, its Chalcogenide Derivatives and Molybdenum(0) Complex

Sarıöz

Çırak

Muradoğlu

et al. 2014

Phosphorus, Sulfur, and Silicon and the Related Elements

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Mo(CO) 4 byp P N H 2 O 2 /S 8 /Se N P E P CO Mo CO CO CO N P N E=O (2), S (3), Se (4) 2-4 5 1 Abstract Functionalized monoaminophosphine PPh 2 NC 5 H 9 CH 2 C 6 H 5 has been synthesized by treating Ph 2 PCl with 4-benzylpiperidine. The ligand reacts with aqueous hydrogen peroxide, elemental sulfur or selenium to give the corresponding chalcogenides in good yield. The molybdenum complex of the aminophosphine has been obtained. All of the new compounds were obtained in good yields and were characterized by IR, NMR, elemental analysis. Theoretical calculations were carried out by using the Hartree-Fock and density functional methods with the 6-31G(d) basis set.

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Metal−Phosphorus Bonding in Fe(CO)₄PR₃ Complexes. A Density Functional Study

Cited by 61 publications

References 70 publications

Ligand Site Preference in Iron Tetracarbonyl Complexes Fe(CO) ₄ L (L = CO, CS, N ₂ , NO ⁺ , CN ^– , NC ^– , η ² ‐C ₂ H ₄ , η ² ‐C ₂ H ₂

Ligand Site Preference in Iron Tetracarbonyl Complexes Fe(CO) ₄ L (L = CO, CS, N ₂ , NO ⁺ , CN ^– , NC ^– , η ² ‐C ₂ H ₄ , η ² ‐C ₂ H ₂

Insertion reaction of propene into Rh?H bond in HRh(CO)(PH3)2(C3H6) compound: A density functional study

Synthesis, Characterization and Ab Initio Calculations of Aminophosphine Derived From 4-Benzylpiperidine, its Chalcogenide Derivatives and Molybdenum(0) Complex

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Metal−Phosphorus Bonding in Fe(CO)4PR3 Complexes. A Density Functional Study

Cited by 61 publications

References 70 publications

Ligand Site Preference in Iron Tetracarbonyl Complexes Fe(CO) 4 L (L = CO, CS, N 2 , NO + , CN – , NC – , η 2 ‐C 2 H 4 , η 2 ‐C 2 H 2

Ligand Site Preference in Iron Tetracarbonyl Complexes Fe(CO) 4 L (L = CO, CS, N 2 , NO + , CN – , NC – , η 2 ‐C 2 H 4 , η 2 ‐C 2 H 2

Insertion reaction of propene into Rh?H bond in HRh(CO)(PH3)2(C3H6) compound: A density functional study

Synthesis, Characterization and Ab Initio Calculations of Aminophosphine Derived From 4-Benzylpiperidine, its Chalcogenide Derivatives and Molybdenum(0) Complex

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Metal−Phosphorus Bonding in Fe(CO)₄PR₃ Complexes. A Density Functional Study

Ligand Site Preference in Iron Tetracarbonyl Complexes Fe(CO) ₄ L (L = CO, CS, N ₂ , NO ⁺ , CN ^– , NC ^– , η ² ‐C ₂ H ₄ , η ² ‐C ₂ H ₂

Ligand Site Preference in Iron Tetracarbonyl Complexes Fe(CO) ₄ L (L = CO, CS, N ₂ , NO ⁺ , CN ^– , NC ^– , η ² ‐C ₂ H ₄ , η ² ‐C ₂ H ₂