2008
DOI: 10.1021/ja808303j
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The QTAIM Approach to Chemical Bonding Between Transition Metals and Carbocyclic Rings: A Combined Experimental and Theoretical Study of (η5-C5H5)Mn(CO)3, (η6-C6H6)Cr(CO)3, and (E)-{(η5-C5H4)CF═CF(η5-C5H4)}(η5-C5H5)2Fe2

Abstract: Experimental charge densities for (C(5)H(5))Mn(CO)(3) (2), (eta(6)-C(6)H(6))Cr(CO)(3) (3), and (E)-{(eta(5)-C(5)H(4))CF=CF(eta(5)-C(5)H(4))}(eta(5)-C(5)H(5))(2)Fe(2) (4) have been obtained by multipole refinement of high-resolution X-ray diffraction data at 100 K. The resultant densities were analyzed using the quantum theory of atoms in molecules (QTAIM). The electronic structures of these and related pi-hydrocarbyl complexes have also been studied by ab initio density functional theory calculations, and a ge… Show more

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Cited by 177 publications
(135 citation statements)
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“…The DED distribution in the region of the dicarbollide anion ( Figure 2, Figure S2 in the Supporting Information) exhibits electron delocalization over the surface of the polyhedron, typical for 12-vertex C-phenylated ortho- [44] and nido-carboranes, [45] and is virtually identical with that in metallocenes or in sandwich or half-sandwich transitionmetal complexes. [28,[46][47][48][49] Slight differences in the peak heights in the B-B and C-C bonds and the shift of the DED maxima in the B-C bonds toward the carbon atoms are associated with polarization of electron density by the more electronegative carbon atoms. Regardless of these differences, the open face of the dicarbollide dianion is analogous (isolobal) to the Cp ligand.…”
Section: Bonding Situationmentioning
confidence: 99%
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“…The DED distribution in the region of the dicarbollide anion ( Figure 2, Figure S2 in the Supporting Information) exhibits electron delocalization over the surface of the polyhedron, typical for 12-vertex C-phenylated ortho- [44] and nido-carboranes, [45] and is virtually identical with that in metallocenes or in sandwich or half-sandwich transitionmetal complexes. [28,[46][47][48][49] Slight differences in the peak heights in the B-B and C-C bonds and the shift of the DED maxima in the B-C bonds toward the carbon atoms are associated with polarization of electron density by the more electronegative carbon atoms. Regardless of these differences, the open face of the dicarbollide dianion is analogous (isolobal) to the Cp ligand.…”
Section: Bonding Situationmentioning
confidence: 99%
“…In this method, topological analysis of the three-dimensional ED is carried out to divide space into atomic basins with surfaces of zero electronic flux. The presence of a bond is associated with the appearance of the bond critical point (bcp), the saddle point in the scalar field of the ED, but one should take into account that QTAIM topology may show ambiguities in bonding scenarios of molecular species with delocalized charge density, such as sandwich or half-sandwich transition-metal complexes [28] and polyhedral boranes [29,30] that are recognized having delocalized charge density. Moreover, the resulting atomic connectivity for such compounds can depend on the quality of experimental data or the DFT functional in theoretical calculations.…”
Section: Introductionmentioning
confidence: 99%
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“…By introduction of surfaces of zero electron flux (zfs), atomic basins and a corresponding bond‐paths pattern are generated; this provides a straightforward interpretation scheme of atomic and bond properties. However, it turned out that the bond‐path analysis, which unambiguously reflects the molecular structure for simple organic compounds, has some limitations for complex bonding scenarios, such as metal–metal bonds,23 borane cages,24 and metallocenes 25. Nowadays, new tools such as the source function (SF),26, 27 and the ELI‐D are available; this promises deeper understanding of chemical interactions.…”
Section: Introductionmentioning
confidence: 99%
“…15 Similarly, unstable bond paths have already been observed in numerous transition-metal complexes. 82,83 4.4. Bond Properties at Rhodium.…”
Section: Molecular Graphsmentioning
confidence: 99%