The Rich Structural Chemistry Displayed by the Carbon Monoxide as a Ligand to Metal Complexes

Ding, Shengda; Hall, Michael B.

doi:10.1007/430_2015_208

Cited by 11 publications

(8 citation statements)

References 117 publications

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“…The compounds synthesized with the end-on π-acceptor ligands CO, CN – , and CNXylyl should differ for each ligand in the electron-richness of the metal center and the back-donation contribution. It is well-known for CO complexes that the more back-donation the CO receives, the lower its IR frequency . This is clearly reflected in the IR stretching frequencies of the CO group of the carbonyl complexes, collected in Table .…”

Section: Results and Discussionmentioning

confidence: 99%

Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*M^III(L)XY] (M = Rh, Ir) Complexes with CO, CN^–, and CNR Ligands. A Window to Cis Influence

et al. 2021

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Analysis of the bonding contributions in molecules [M III Cp*(L)XY] (M = Rh, Ir; Cp* = C 5 Me 5 ; L = CO, CN − , CNR) has uncovered a rich variety of types of interaction that seem to have escaped detection so far, in spite of the continuous popularity of cyclopentadienyl transition-metal complexes since the 1970s. At variance with the MCO bond in square-planar systems, which shows typical metal-to-CO π-back-donation, the nonorthogonal arrangement of the Cp* plane and RhCO fragment and the pseudooctahedral geometry lead to the observation of many direct lateral donations from other ligands that do not involve the metal orbitals, and we name side donations, for instance, Cp* → π*(CO), Cl → π*(CO), and F → π*(CO). Hybrid donations partially involving the metal, M−C aryl → π*(CO), are also observed. The summation of multiple contributions other than back-donation can easily account for about 20% of the electron donation to the π*(CO) orbitals.

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Section: Results and Discussionmentioning

confidence: 99%

Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*M^III(L)XY] (M = Rh, Ir) Complexes with CO, CN^–, and CNR Ligands. A Window to Cis Influence

et al. 2021

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“…However, molecular orbital (MO) analysis and the calculated negative value of the Fe–Fe overlap population suggest that there is no Fe–Fe bond. ,− This is supported by a quantum theory of atoms-in-molecules (QTAIM) analysis, which shows the absence of an Fe–Fe bond path, and by the analysis of the domain-averaged Fermi holes in Fe 2 (CO) 9 . The present understanding of the bonding situation in Fe 2 (CO) 9 was recently reviewed by Ding and Hall . The 18-electron rule is fulfilled either by assuming an Fe–Fe bond or by formally considering different bonding interactions of the three bridging CO ligands, where one of them engages in a three-center two-electron bond, while the other two are ketonic groups that are bonded via Fe−C electron-sharing bonds (Figure ).…”

Section: Introductionmentioning

confidence: 95%

“…It means that the bridging CO ligands donate on average more electrons to iron than the terminal CO groups. Ding and Hall also present an MO correlation diagram, where the relevant orbitals of Fe 2 (CO) 9 are constructed from scratch, using the orbitals of Fe and CO as building blocks, which eventually lead to the full MO diagram of the complex . The fairly elaborate analysis shows that the descriptive qualitative MO explanation for the bonding in Fe 2 (CO) 9 is quite complicated.…”

Section: Introductionmentioning

confidence: 99%

Bonding in Binuclear Carbonyl Complexes M₂(CO)₉(M = Fe, Ru, Os)

et al. 2018

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Quantum-chemical density functional theory calculations using the BP86 functional in conjunction with a triple-ζ basis set and dispersion correction by Grimme with Becke-Johnson damping D3(BJ) were performed for the title molecules. The nature of the bonding was examined with the quantum theory of atoms in molecules (QTAIM) and natural bond order (NBO) methods and with the energy decomposition analysis in conjunction with the natural orbital for chemical valence (EDA-NOCV) analysis. The energetically lowest-lying form of Fe(CO) is the triply bridged D structure, whereas the most stable structures of Ru(CO) and Os(CO) are singly bridged C species. The calculated reaction energies for the formation of the cyclic trinuclear carbonyls M(CO) from the dinuclear carbonyls M(CO) are in agreement with experiment, as the iron complex Fe(CO) is thermodynamically stable in these reactions, but the heavier homologues Ru(CO) and Os(CO) are not. The metal-CO bond to the bridging CO ligands is stronger than the bonds to the terminal CO ligands. This holds for the triply bridged D structures as well as for the singly bridged C or C species. The analysis of the orbital interactions with the help of the EDA-NOCV method suggests that the overall M→CO π backdonation is always stronger than the M←CO σ donation. The bridging carbonyls are more strongly bonded than the terminal CO ligands, and they are engaged in stronger σ donation and π backdonation, but the formation of bridging carbonyls requires reorganization energy, which may or may not be compensated by the stronger metal-ligand interactions. The lower-lying D form of Fe(CO) and C structures of Ru(CO) and Os(CO) are due to a delicate balance of several forces.

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“…In connection with the 18-electron rule an electron count of 17 ve attributed to a Fe center is consistent with the formation of an Fe–Fe bond. However, the famous example of Fe 2 (CO) 9 with three bridging CO groups , is reminiscent of the alternative possibility of three-center Fe–C–Fe bonding instead of pure two-center Fe–Fe and Fe–C bonds. The gross scenario discussed there features a mixture of two-center Fe–C and three-center Fe–C–Fe bonding, where direct Fe–Fe bonding does not occur.…”

Section: Resultsmentioning

confidence: 99%

On Fe–Fe Dumbbells in the Ideal and Real Structures of FeGa₃

et al. 2018

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The intermetallic phase FeGa3 belongs to the rare examples of substances with transition metals where semiconducting behavior is found. The necessary electron count of 17 ve/fu can be formally derived from eight Fe–Ga and one Fe–Fe two-center–two-electron bond. The situation is reminiscent of the well-known Fe2(CO)9 scenario, where a direct Fe–Fe two-center–two-electron bond was shown to not be present. Fe–Fe interaction in FeGa3 and its substitution variants represents the crucial point for explanation of electronic, thermal transport, and optical properties of this material. Chemical bonding analysis in position space of FeGa3 and Fe2(CO)9 on the basis of the topology of the electron localizability indicator distribution, QTAIM atoms, two- and three-center delocalization indices, domain natural orbitals, IQA analysis, and an evaluation of the Fe–Fe dissociation energy yields a complete picture of the partially compensated Fe–Fe bond, which is nevertheless strong enough to be of decisive importance. Structural reinvestigation of differently synthesized single crystals leads to the composition Fe1+x Ga3 (0 ≤ x ≤ 0.018), where the additional Fe atoms are predicted from DFT/PBE calculations to yield a magnetic moment of about 2 μB/Fe2 atom and metallic in-gap states. Accompanying magnetization and ESR measurements are consistent with this picture.

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The Rich Structural Chemistry Displayed by the Carbon Monoxide as a Ligand to Metal Complexes

Cited by 11 publications

References 117 publications

Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*M^III(L)XY] (M = Rh, Ir) Complexes with CO, CN^–, and CNR Ligands. A Window to Cis Influence

Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*M^III(L)XY] (M = Rh, Ir) Complexes with CO, CN^–, and CNR Ligands. A Window to Cis Influence

Bonding in Binuclear Carbonyl Complexes M₂(CO)₉(M = Fe, Ru, Os)

On Fe–Fe Dumbbells in the Ideal and Real Structures of FeGa₃

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The Rich Structural Chemistry Displayed by the Carbon Monoxide as a Ligand to Metal Complexes

Cited by 11 publications

References 117 publications

Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*MIII(L)XY] (M = Rh, Ir) Complexes with CO, CN–, and CNR Ligands. A Window to Cis Influence

Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*MIII(L)XY] (M = Rh, Ir) Complexes with CO, CN–, and CNR Ligands. A Window to Cis Influence

Bonding in Binuclear Carbonyl Complexes M2(CO)9(M = Fe, Ru, Os)

On Fe–Fe Dumbbells in the Ideal and Real Structures of FeGa3

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Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*M^III(L)XY] (M = Rh, Ir) Complexes with CO, CN^–, and CNR Ligands. A Window to Cis Influence

Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*M^III(L)XY] (M = Rh, Ir) Complexes with CO, CN^–, and CNR Ligands. A Window to Cis Influence

Bonding in Binuclear Carbonyl Complexes M₂(CO)₉(M = Fe, Ru, Os)

On Fe–Fe Dumbbells in the Ideal and Real Structures of FeGa₃