NHC‐Stabilised Acetylene—How Far Can the Analogy Be Pushed?

Georgiou, Dayne C.; Zhao, Lili; Wilson, David J.; Frenking, Gernot; Dutton, Jason L.

doi:10.1002/chem.201605495

Cited by 68 publications

(39 citation statements)

References 111 publications

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“…nature is not directly apparent. [27][28][29][30][31][32][33][34][35][36][37] Tables S4-S6 show that the DE orb values using atom Minthe electronic ground state and (Bz) 3 in the excited state are significantly larger than those in Table 4. However,t here is an alternative option for the choice of the interacting fragments.T he calculated partial charges of M(Bz) 3 using the NBO 6.0 method [38] suggest large positive charges for the metal atoms of 1.47 for Ca, 1.46 for Sr and 1.40 for Ba.…”

Section: Termmentioning

confidence: 87%

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Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)₃(M=Sr, Ba)

Wang

Pan

et al. 2019

Angew Chem Int Ed

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We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)3 (M=Sr, Ba) in low‐temperature Ne matrix. Both complexes are characterized by a D3 symmetric structure involving three equivalent η6‐bound benzene ligands and a closed‐shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal–ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the π MOs of benzene ligands into the vacant (n−1)d AOs of M and strong backdonation from the occupied (n−1)d AO of M into vacant π* MOs of benzene ligands. The metals in these 20‐electron complexes have 18 effective valence electrons, and, thus, fulfill the 18‐electron rule if only the metal–ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals.

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Section: Termmentioning

confidence: 87%

“…Our experience in numerous studies has shown that the EDA-NOCV calculations are not very sensitive to the functional. [27][28][29][30][31][32][33][34][35][36][37] Table 4gives the numerical results of the calculations of M(Bz) 3 (M = Ca, Sr, Ba) at the D 3 equilibrium structures.…”

Section: Modementioning

confidence: 99%

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)₃(M=Sr, Ba)

Wang

Pan

et al. 2019

Angew Chem Int Ed

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“…The method has been found useful in several molecules where the nature of the bonding interactions is not obvious. The reader may find further examples in the literature …”

Section: The Eda–nocv Methodsmentioning

confidence: 99%

Energy decomposition analysis

Zhao

Hopffgarten

Andrada

et al. 2017

WIREs Comput Mol Sci

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“…Those fragments, which yield the smallest orbital interaction energy, indicate the most faithful model for the bonding situation. This was particularly useful in cases for which the description in terms of dative bonds A→B or electron‐sharing bonds A−B was not clear ,…”

Section: Introductionmentioning

confidence: 99%

Dative and Electron‐Sharing Bonding in C₂F₄

Andrada

Casals‐Sainz

Pendás

et al. 2018

Chemistry A European J

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The reaction pathway for the rupture of the carbon-carbon double bond of C F has been calculated with ab initio methods at the CASSCF(8,8)+NEVPT2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ levels and with density functional theory using M06-L and M06-2X functionals in conjunction with aug-cc-pVTZ basis sets. The calculations suggest that the bond dissociation pathway proceeds by a nonlinear reaction course without an activation barrier yielding the CF fragments in the ( A ) ground state. A bonding analysis indicates that there is a continuous change in the electronic structure of the CF fragments during the elongation of the C-C distance from a ( B ) excited state at the equilibrium geometry of C F to the ( A ) ground state. EDA-NOCV calculations suggest that the carbon-carbon interactions in C F at equilibrium distance and longer C-C values up to ≈1.60 Å are best described in terms of electron-sharing bonding between the CF fragments in the ( B ) excited state. At longer distances, the situation changes toward dative bonding between CF fragments in the ( A ) ground state.

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NHC‐Stabilised Acetylene—How Far Can the Analogy Be Pushed?

Cited by 68 publications

References 111 publications

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)₃(M=Sr, Ba)

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)₃(M=Sr, Ba)

Energy decomposition analysis

Dative and Electron‐Sharing Bonding in C₂F₄

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NHC‐Stabilised Acetylene—How Far Can the Analogy Be Pushed?

Cited by 68 publications

References 111 publications

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)3(M=Sr, Ba)

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)3(M=Sr, Ba)

Energy decomposition analysis

Dative and Electron‐Sharing Bonding in C2F4

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Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)₃(M=Sr, Ba)

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)₃(M=Sr, Ba)

Dative and Electron‐Sharing Bonding in C₂F₄