Comparative Experimental and Theoretical Study of the Fe L 2,3 -Edges X-ray Absorption Spectroscopy in Three Highly Popular, Low-Spin Organoiron Complexes: [Fe(CO) 5 ], [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 , and [(η 5 -C 5 H 5 ) 2 Fe]

Girolamo Casella, Silvia Carlotto, Marcello Coreno, Mauro Sambi, Maurizio Casarin, Paola Finetti, Monica De Simone

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Abstract

The occupied and unoccupied electronic structures of three highly popular, closed shell organoiron complexes ([Fe(CO) 5 ], [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 , and [(η 5 -C 5 H 5 ) 2 Fe]) have been theoretically investigated by taking advantage of density functional theory (DFT) calculations coupled to the isolobal analogy (Elian et al. Inorg. Chem. 1976, 15, 1148). The adopted approach allowed us to look into the relative role played by the ligand → Fe donation and the Fe → ligand back-donation in title molecules, as well as to investigate how CO- (terminal or bridging) and [(η 5 -C 5 H 5 )] - -based π∗ orbitals compete when these two ligands are simultaneously present as in [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 . Insights into the nature and the strength of the bonding between Fe and the C donor atoms have been gained by exploiting the Nalewajski-Mrozek bond multiplicity index (Nalewajski et al. Int. J. Quantum Chem. 1994, 51, 187), which have been found especially sensitive even to tiny bond distance variations. The bonding picture emerging from ground state DFT results proved fruitful to guide the assignment of original, high-resolution, gas-phase L 2,3 -edges X-ray absorption spectra of the title molecules, which have been modeled by the two-component relativistic time-dependent DFT including spin orbit coupling and correlation effects and taking advantage of the full use of symmetry. Assignments alternative to those reported in the literature for both [Fe(CO) 5 ] and [(η 5 -C 5 H 5 ) 2 Fe] are herein proposed. Despite the high popularity of the investigated molecules, the complementary use of symmetry, orbital, and spectroscopy allowed us to further look into the metal-ligand symmetry-restricted-covalency and the differential-orbital covalency, which characterize them. ©
Lingua originaleEnglish
pagine (da-a)5844-5857
Numero di pagine14
RivistaInorganic Chemistry
Volume58
Stato di pubblicazionePublished - 2019

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X ray absorption spectroscopy
absorption spectroscopy
Ligands
Density functional theory
ligands
density functional theory
orbitals
Molecules
symmetry
x rays
Shells (structures)
molecules
X ray absorption
Carbon Monoxide
Ground state
Electronic structure
Absorption spectra
emerging
Orbits
Gases

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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@article{58c3dd33519e44469a3edf4d4f96e982,
title = "Comparative Experimental and Theoretical Study of the Fe L 2,3 -Edges X-ray Absorption Spectroscopy in Three Highly Popular, Low-Spin Organoiron Complexes: [Fe(CO) 5 ], [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 , and [(η 5 -C 5 H 5 ) 2 Fe]",
abstract = "The occupied and unoccupied electronic structures of three highly popular, closed shell organoiron complexes ([Fe(CO) 5 ], [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 , and [(η 5 -C 5 H 5 ) 2 Fe]) have been theoretically investigated by taking advantage of density functional theory (DFT) calculations coupled to the isolobal analogy (Elian et al. Inorg. Chem. 1976, 15, 1148). The adopted approach allowed us to look into the relative role played by the ligand → Fe donation and the Fe → ligand back-donation in title molecules, as well as to investigate how CO- (terminal or bridging) and [(η 5 -C 5 H 5 )] - -based π∗ orbitals compete when these two ligands are simultaneously present as in [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 . Insights into the nature and the strength of the bonding between Fe and the C donor atoms have been gained by exploiting the Nalewajski-Mrozek bond multiplicity index (Nalewajski et al. Int. J. Quantum Chem. 1994, 51, 187), which have been found especially sensitive even to tiny bond distance variations. The bonding picture emerging from ground state DFT results proved fruitful to guide the assignment of original, high-resolution, gas-phase L 2,3 -edges X-ray absorption spectra of the title molecules, which have been modeled by the two-component relativistic time-dependent DFT including spin orbit coupling and correlation effects and taking advantage of the full use of symmetry. Assignments alternative to those reported in the literature for both [Fe(CO) 5 ] and [(η 5 -C 5 H 5 ) 2 Fe] are herein proposed. Despite the high popularity of the investigated molecules, the complementary use of symmetry, orbital, and spectroscopy allowed us to further look into the metal-ligand symmetry-restricted-covalency and the differential-orbital covalency, which characterize them. {\circledC}",
author = "Girolamo Casella and Silvia Carlotto and Marcello Coreno and Mauro Sambi and Maurizio Casarin and Paola Finetti and {De Simone}, Monica",
year = "2019",
language = "English",
volume = "58",
pages = "5844--5857",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",

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TY - JOUR

T1 - Comparative Experimental and Theoretical Study of the Fe L 2,3 -Edges X-ray Absorption Spectroscopy in Three Highly Popular, Low-Spin Organoiron Complexes: [Fe(CO) 5 ], [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 , and [(η 5 -C 5 H 5 ) 2 Fe]

AU - Casella, Girolamo

AU - Carlotto, Silvia

AU - Coreno, Marcello

AU - Sambi, Mauro

AU - Casarin, Maurizio

AU - Finetti, Paola

AU - De Simone, Monica

PY - 2019

Y1 - 2019

N2 - The occupied and unoccupied electronic structures of three highly popular, closed shell organoiron complexes ([Fe(CO) 5 ], [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 , and [(η 5 -C 5 H 5 ) 2 Fe]) have been theoretically investigated by taking advantage of density functional theory (DFT) calculations coupled to the isolobal analogy (Elian et al. Inorg. Chem. 1976, 15, 1148). The adopted approach allowed us to look into the relative role played by the ligand → Fe donation and the Fe → ligand back-donation in title molecules, as well as to investigate how CO- (terminal or bridging) and [(η 5 -C 5 H 5 )] - -based π∗ orbitals compete when these two ligands are simultaneously present as in [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 . Insights into the nature and the strength of the bonding between Fe and the C donor atoms have been gained by exploiting the Nalewajski-Mrozek bond multiplicity index (Nalewajski et al. Int. J. Quantum Chem. 1994, 51, 187), which have been found especially sensitive even to tiny bond distance variations. The bonding picture emerging from ground state DFT results proved fruitful to guide the assignment of original, high-resolution, gas-phase L 2,3 -edges X-ray absorption spectra of the title molecules, which have been modeled by the two-component relativistic time-dependent DFT including spin orbit coupling and correlation effects and taking advantage of the full use of symmetry. Assignments alternative to those reported in the literature for both [Fe(CO) 5 ] and [(η 5 -C 5 H 5 ) 2 Fe] are herein proposed. Despite the high popularity of the investigated molecules, the complementary use of symmetry, orbital, and spectroscopy allowed us to further look into the metal-ligand symmetry-restricted-covalency and the differential-orbital covalency, which characterize them. ©

AB - The occupied and unoccupied electronic structures of three highly popular, closed shell organoiron complexes ([Fe(CO) 5 ], [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 , and [(η 5 -C 5 H 5 ) 2 Fe]) have been theoretically investigated by taking advantage of density functional theory (DFT) calculations coupled to the isolobal analogy (Elian et al. Inorg. Chem. 1976, 15, 1148). The adopted approach allowed us to look into the relative role played by the ligand → Fe donation and the Fe → ligand back-donation in title molecules, as well as to investigate how CO- (terminal or bridging) and [(η 5 -C 5 H 5 )] - -based π∗ orbitals compete when these two ligands are simultaneously present as in [(η 5 -C 5 H 5 )Fe(CO)(μ-CO)] 2 . Insights into the nature and the strength of the bonding between Fe and the C donor atoms have been gained by exploiting the Nalewajski-Mrozek bond multiplicity index (Nalewajski et al. Int. J. Quantum Chem. 1994, 51, 187), which have been found especially sensitive even to tiny bond distance variations. The bonding picture emerging from ground state DFT results proved fruitful to guide the assignment of original, high-resolution, gas-phase L 2,3 -edges X-ray absorption spectra of the title molecules, which have been modeled by the two-component relativistic time-dependent DFT including spin orbit coupling and correlation effects and taking advantage of the full use of symmetry. Assignments alternative to those reported in the literature for both [Fe(CO) 5 ] and [(η 5 -C 5 H 5 ) 2 Fe] are herein proposed. Despite the high popularity of the investigated molecules, the complementary use of symmetry, orbital, and spectroscopy allowed us to further look into the metal-ligand symmetry-restricted-covalency and the differential-orbital covalency, which characterize them. ©

UR - http://hdl.handle.net/10447/365603

UR - https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.9b00226

M3 - Article

VL - 58

SP - 5844

EP - 5857

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

ER -