Cluster carbonyls of the [Re63-Se) 8]2+ core: Synthesis, structural characterization, and computational analysis

Peter J. Orto, Gary S. Nichol, Noriko Okumura, Dennis H. Evans, Ramiro Arratia-Pérez, Rodrigo Ramirez-Tagle, Ruiyao Wang, Zhiping Zheng

Research output: Contribution to journalArticle

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Abstract

The reactions of the previously reported cluster complexes [Re 63-Se)8(PEt3)5I]I, trans-[Re63-Se)8(PEt3) 4I2], and cis-[Re63-Se) 8(PEt3)4I2] with the [Re 63-Se)8]2+ core with CO in the presence of AgSbF6 afforded the corresponding cluster carbonyls [Re63-Se)8(PEt3) 5(CO)][SbF6]2 (1), trans-[Re 63-Se)8(PEt3) 4(CO)2][SbF6]2 (2), and cis-[Re 63-Se)8(PEt3) 4(CO)2][SbF6]2 (3). Infrared spectroscopy indicated weakening of the bond in CO, suggesting the existence of backbonding between the cluster core and the CO ligand(s). Electrochemical studies focusing on the reversible, one-electron oxidation of the cluster core revealed a large increase in the oxidation potential upon going from the acetonitrile derivatives to their carbonyl analogs, consistent with the depleted electron density of the cluster core upon CO ligation. Disparities between the IR spectra and oxidation potential between 2 and 3 indicate that electronic differences exist between sites trans and cis to the location of a ligand of interest. The active role played by the Se atoms in influencing the cluster-to-CO bonding interactions is suggested through this result and density functional (DF) computational analysis. The computations indicate that molecular orbitals near the HOMO account for backbonding interactions with a high percentage of participation of Se orbitals.

Original languageEnglish (US)
Pages (from-to)4247-4253
Number of pages7
JournalDalton Transactions
Issue number32
DOIs
StatePublished - 2008

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Carbon Monoxide
Oxidation
Ligands
Molecular orbitals
Carrier concentration
Infrared spectroscopy
Derivatives
Atoms
Electrons

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Orto, P. J., Nichol, G. S., Okumura, N., Evans, D. H., Arratia-Pérez, R., Ramirez-Tagle, R., ... Zheng, Z. (2008). Cluster carbonyls of the [Re63-Se) 8]2+ core: Synthesis, structural characterization, and computational analysis. Dalton Transactions, (32), 4247-4253. https://doi.org/10.1039/b806973e

Cluster carbonyls of the [Re63-Se) 8]2+ core : Synthesis, structural characterization, and computational analysis. / Orto, Peter J.; Nichol, Gary S.; Okumura, Noriko; Evans, Dennis H.; Arratia-Pérez, Ramiro; Ramirez-Tagle, Rodrigo; Wang, Ruiyao; Zheng, Zhiping.

In: Dalton Transactions, No. 32, 2008, p. 4247-4253.

Research output: Contribution to journalArticle

Orto, PJ, Nichol, GS, Okumura, N, Evans, DH, Arratia-Pérez, R, Ramirez-Tagle, R, Wang, R & Zheng, Z 2008, 'Cluster carbonyls of the [Re63-Se) 8]2+ core: Synthesis, structural characterization, and computational analysis', Dalton Transactions, no. 32, pp. 4247-4253. https://doi.org/10.1039/b806973e
Orto, Peter J. ; Nichol, Gary S. ; Okumura, Noriko ; Evans, Dennis H. ; Arratia-Pérez, Ramiro ; Ramirez-Tagle, Rodrigo ; Wang, Ruiyao ; Zheng, Zhiping. / Cluster carbonyls of the [Re63-Se) 8]2+ core : Synthesis, structural characterization, and computational analysis. In: Dalton Transactions. 2008 ; No. 32. pp. 4247-4253.
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title = "Cluster carbonyls of the [Re6(μ3-Se) 8]2+ core: Synthesis, structural characterization, and computational analysis",
abstract = "The reactions of the previously reported cluster complexes [Re 6(μ3-Se)8(PEt3)5I]I, trans-[Re6(μ3-Se)8(PEt3) 4I2], and cis-[Re6(μ3-Se) 8(PEt3)4I2] with the [Re 6(μ3-Se)8]2+ core with CO in the presence of AgSbF6 afforded the corresponding cluster carbonyls [Re6(μ3-Se)8(PEt3) 5(CO)][SbF6]2 (1), trans-[Re 6(μ3-Se)8(PEt3) 4(CO)2][SbF6]2 (2), and cis-[Re 6(μ3-Se)8(PEt3) 4(CO)2][SbF6]2 (3). Infrared spectroscopy indicated weakening of the bond in CO, suggesting the existence of backbonding between the cluster core and the CO ligand(s). Electrochemical studies focusing on the reversible, one-electron oxidation of the cluster core revealed a large increase in the oxidation potential upon going from the acetonitrile derivatives to their carbonyl analogs, consistent with the depleted electron density of the cluster core upon CO ligation. Disparities between the IR spectra and oxidation potential between 2 and 3 indicate that electronic differences exist between sites trans and cis to the location of a ligand of interest. The active role played by the Se atoms in influencing the cluster-to-CO bonding interactions is suggested through this result and density functional (DF) computational analysis. The computations indicate that molecular orbitals near the HOMO account for backbonding interactions with a high percentage of participation of Se orbitals.",
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AU - Evans, Dennis H.

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N2 - The reactions of the previously reported cluster complexes [Re 6(μ3-Se)8(PEt3)5I]I, trans-[Re6(μ3-Se)8(PEt3) 4I2], and cis-[Re6(μ3-Se) 8(PEt3)4I2] with the [Re 6(μ3-Se)8]2+ core with CO in the presence of AgSbF6 afforded the corresponding cluster carbonyls [Re6(μ3-Se)8(PEt3) 5(CO)][SbF6]2 (1), trans-[Re 6(μ3-Se)8(PEt3) 4(CO)2][SbF6]2 (2), and cis-[Re 6(μ3-Se)8(PEt3) 4(CO)2][SbF6]2 (3). Infrared spectroscopy indicated weakening of the bond in CO, suggesting the existence of backbonding between the cluster core and the CO ligand(s). Electrochemical studies focusing on the reversible, one-electron oxidation of the cluster core revealed a large increase in the oxidation potential upon going from the acetonitrile derivatives to their carbonyl analogs, consistent with the depleted electron density of the cluster core upon CO ligation. Disparities between the IR spectra and oxidation potential between 2 and 3 indicate that electronic differences exist between sites trans and cis to the location of a ligand of interest. The active role played by the Se atoms in influencing the cluster-to-CO bonding interactions is suggested through this result and density functional (DF) computational analysis. The computations indicate that molecular orbitals near the HOMO account for backbonding interactions with a high percentage of participation of Se orbitals.

AB - The reactions of the previously reported cluster complexes [Re 6(μ3-Se)8(PEt3)5I]I, trans-[Re6(μ3-Se)8(PEt3) 4I2], and cis-[Re6(μ3-Se) 8(PEt3)4I2] with the [Re 6(μ3-Se)8]2+ core with CO in the presence of AgSbF6 afforded the corresponding cluster carbonyls [Re6(μ3-Se)8(PEt3) 5(CO)][SbF6]2 (1), trans-[Re 6(μ3-Se)8(PEt3) 4(CO)2][SbF6]2 (2), and cis-[Re 6(μ3-Se)8(PEt3) 4(CO)2][SbF6]2 (3). Infrared spectroscopy indicated weakening of the bond in CO, suggesting the existence of backbonding between the cluster core and the CO ligand(s). Electrochemical studies focusing on the reversible, one-electron oxidation of the cluster core revealed a large increase in the oxidation potential upon going from the acetonitrile derivatives to their carbonyl analogs, consistent with the depleted electron density of the cluster core upon CO ligation. Disparities between the IR spectra and oxidation potential between 2 and 3 indicate that electronic differences exist between sites trans and cis to the location of a ligand of interest. The active role played by the Se atoms in influencing the cluster-to-CO bonding interactions is suggested through this result and density functional (DF) computational analysis. The computations indicate that molecular orbitals near the HOMO account for backbonding interactions with a high percentage of participation of Se orbitals.

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