Application of the multiple scattering X.alpha. molecular orbital method to the determination of the electronic structure of metallocene compounds. 1. Dibenzenechromium and its cation

Weber, Jacques; Geoffroy, Michel; Goursot, Annick; Pénigault, E.

doi:10.1021/ja00481a003

Cited by 76 publications

(45 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In view of the large difference in intersphere volumes in both compounds, one may indeed ask whether the attribution of the whole intersphere charge to the ligands is a realistic procedure and, consequently, whether the different charges on metal obtained for 1 and 2 are not an artifact of the calculation. As another, significantly different, charge partition scheme, we decided to use the alternative of distributing for each MO the interatomic charge among all atoms in the molecule proportionally to the amount of orbital charge (originating from-this orbital) included in each sphere (6). This procedure leads to the 1.e.…”

Section: Methodsmentioning

confidence: 99%

“…It was therefore of interest to perform a comparative theoretical study of the electronic structure of 1 and 2 in an attempt to understand the different properties of these compounds. To this end, the multiple scattering (MS) Xa molecular orbital (MO) model was chosen since it has been previously shown to give reliable predictions of the electronic structure and related properties of organometallic compounds such as 1 (6) or several members of the metallocene series (7)(8)(9)(10)(11).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

Weber¹,

Kündig²,

Goursot³

et al. 1985

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

. SCF MS X a molecular orbital calculations are reported for the bis(q"benzene)-and bis(q6-naphthalene)chromium (O) complexes. The bonding may be essentially discussed in terms of the covalent interactions between the metal 3d and ligand .rr and .rr* orbitals. The different charges on chromium atom in the two systems are explained by the different balances between ligand-to-metal (bonding) and metal-to-ligand (back-bonding) electron donations. Some resemblances are found between the electronic structures of the two compounds and it is possible to correlate to a large extent the energy levels of their molecular orbitals. However, a shift towards lower values is predicted for the energy levels of the naphthalene complex, together with a large disruption of all the virtual .rr* and 3d* levels. This would undoubtedly favor nucleophilic attack followed by metal-ring or carbon-carbon bond cleavage, in agreement with the extreme lability of the coordinated arene rings observed in this complex.JACQUES WEBER, E. PETER KUNDIG, ANNICK GOURSOT et EDOUARD PENIGAULT. Can. J. Chem. 63, 1734Chem. 63, (1985.On a effectuC des calculs d'orbitales molCculaires MS Xa en champ autocohCrent pour les complexes bis(q"benzkne)-et bis(q6-naphtal&ne)chrome(0). On peut decrire la liaison dans le complex presque essentiellement l'aide des interactions covalentes entre les orbitales 3d du metal et les orbitales T et T* du ligand. On explique les diffkrentes charges sur l'atome de chrome dans les deux systemes par des bilans differents entre la donation directe d'klectrons ligand-mCtal et la rCtrodonation mCtal-ligand. Toutefois, on prCdit un dkplacement vers des valeurs plus basses pour les niveaux CnergCtiques du complexe de naphtalene ainsi qu'un mClange important de tous les niveaux virtuels .rr* et 3d*. Ceci devrait de toute evidence favoriser une attaque nuclCophile, suivie d'une rupture de la liaison mCtal-cycle ou carbone-carbone, en accord avec la labilitC extrCme observke dans ces complexes pour les cycles areniques coordonnCs.[Traduit par le journal]

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

Weber¹,

Kündig²,

Goursot³

et al. 1985

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…It is then clear that, for overlapping electronic densities, the average of ( 2 8 ) is now where ql(ra) represents the portion of p charge in the overlap region 1 in Figure 3. For ra < Rap -bp (30) is equal to (29) because ql(ra) = 0 but once ra enters region 1, (30) is slightly greater than (29). This effect is shown in Sec.…”

Section: Pmentioning

confidence: 83%

The MS potential from a set of overlapping densities

Costas¹,

Garritz²

2009

Int. J. Quantum Chem.

View full text Add to dashboard Cite

It is shown that the usual overlapping spheres method must include, in the monoelectronic potential, some overlap terms which are not present in the functional form of the muffin-tin potential. A new truncated spheres approximate projection is presented and compared with other projections which make use of muffin-tin-like potentials. Results are presented for the potential corrections in the atomic region of the H2 molecule and for some transition metal dihalides, where a comparison between the calculated transition state eigenvalues and the experimental photoelectron spectra is presented.

show abstract

“…The electronic structure of bisbenzene chromium has been investigated by different theoretical procedures: semiempirical LCAO models [31,32], ab initio calculations in a near minimal basis [15] and statistical Xa approaches [33]. The INDO results for the high-lying valence orbitals are also Table 1; the geometrical parameters have been adopted from the X-ray data of [34].…”

Section: D5d Aig A2g Eig E2g Aiu A2u Eiu E2umentioning

confidence: 99%

The Electronic Structure of Closed Shell Metallocenes in the Ground State and in the Cationic Hole-States

Böhm

1982

Zeitschrift Für Naturforschung A

View full text Add to dashboard Cite

The electronic structure of tne closed shell metallocenes bis(7r-cyclopentadienyl)magnesium (1), bisbenzene chromium (2), ferrocene (3) and cyclopentadienyl benzene manganese (4) has been studied in the ground state as well as in the low-lying cationic states. The computational framework is a semiempirical INDO Hamiltonian, the theoretical framework for the investigation of the cationic hole-states is the Green's function method. The calculated ionization energies are compared with the photoelectron (PE) spectra of the four closed shell metallocenes. The interrelation between theoretically determined reorganization energies and the localization properties of the orbital wave functions or the nature of the transition metal center is analyzed. General rules concerning the validity of Koopman's theorem in transition metal complexes are formulated.

show abstract

Application of the multiple scattering X.alpha. molecular orbital method to the determination of the electronic structure of metallocene compounds. 1. Dibenzenechromium and its cation

Cited by 76 publications

References 5 publications

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

The MS potential from a set of overlapping densities

The Electronic Structure of Closed Shell Metallocenes in the Ground State and in the Cationic Hole-States

Contact Info

Product

Resources

About

Application of the multiple scattering X.alpha. molecular orbital method to the determination of the electronic structure of metallocene compounds. 1. Dibenzenechromium and its cation

Cited by 76 publications

References 5 publications

The electronic structures of bis(η6-benzene)- and bis(η6-naphthalene)chromium(0)

The electronic structures of bis(η6-benzene)- and bis(η6-naphthalene)chromium(0)

The MS potential from a set of overlapping densities

The Electronic Structure of Closed Shell Metallocenes in the Ground State and in the Cationic Hole-States

Contact Info

Product

Resources

About

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)