Spectroscopic Characterization of $μ$-$η$1:$η$1-Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters

Palermo, Andrew P.; Schöttle, Christian; Zhang, Shengjie; Grosso-Giordano, Nicolás A.; Okrut, Alexander; Dixon, David A.; Frei, Heinz; Gates, Bruce C.; Katz, Alexander

doi:10.1021/acs.inorgchem.9b01529

Title: Spectroscopic Characterization of $$μ$$-$$η$$¹:$$η$$¹-Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters

Abstract

Although oxygen is a common ligand in supported metal catalysts, its coordination has been challenging to elucidate. Herein we characterize a diiridium complex that has been previously shown by X-ray diffraction crystallography to incorporate a μ-η¹:η¹-peroxo ligand. We observe markedly enhanced intensity at 788 cm^-1 in the Raman spectrum of this complex, which is a consequence of bonding of the peroxo ligand but does not shift upon ¹⁸O labeling. Electronic structure calculations at the density functional theory level suggest that this increase in Raman intensity results from bands associated with rocking of CH₂ substituents directly attached to P(Ph)₂ groups coupling with the O-O band. These results provide part of the foundation for understanding oxygen ligands on a silica-supported tetrairidium carbonyl cluster stabilized with bulky electron-donating phosphine ligands [p-tert-butyl-calix[4]arene(OPr)₃(OCH₂PPh₂) (Ph = phenyl; Pr = propyl)]. Reaction of the cluster with O2 also led to the growing in of a Raman band at 788 cm^-1, similar to that in the diiridium complex and also assigned to the bonding of a bridging peroxo ligand. Infrared spectra recorded as the supported cluster reacted in sequential exposures to (i) H₂, (ii) O₂, (iii) H₂, and (iv) CO indicate that two bridging peroxo ligands were bondedmore »« less

Authors:

^[1];

^[2]; Zhang, Shengjie ^[3];

^[2];

^[3];

^[4];

^[1];

^[2]

Univ. of California, Davis, CA (United States)
Univ. of California, Berkeley, CA (United States)
Univ. of Alabama, Tuscaloosa, AL (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: 2019-10-22

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Chevron Corp.; German Research Foundation (DFG)

OSTI Identifier:: 1580967

Grant/Contract Number:: AC02-05CH11231; FG02-04ER15513; FG02-05ER15696

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Volume: 58; Journal Issue: 21; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Anions; Transition metals; Ligands; Cluster chemistry; Metal clusters

Citation Formats


                    Palermo, Andrew P., Schöttle, Christian, Zhang, Shengjie, Grosso-Giordano, Nicolás A., Okrut, Alexander, Dixon, David A., Frei, Heinz, Gates, Bruce C., and Katz, Alexander. Spectroscopic Characterization of $μ$-$η$1:$η$1-Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.inorgchem.9b01529.

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                    Palermo, Andrew P., Schöttle, Christian, Zhang, Shengjie, Grosso-Giordano, Nicolás A., Okrut, Alexander, Dixon, David A., Frei, Heinz, Gates, Bruce C., & Katz, Alexander. Spectroscopic Characterization of $μ$-$η$1:$η$1-Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters.  United States.  https://doi.org/10.1021/acs.inorgchem.9b01529

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                    Palermo, Andrew P., Schöttle, Christian, Zhang, Shengjie, Grosso-Giordano, Nicolás A., Okrut, Alexander, Dixon, David A., Frei, Heinz, Gates, Bruce C., and Katz, Alexander. Tue .  
"Spectroscopic Characterization of $μ$-$η$1:$η$1-Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters".  United States.  https://doi.org/10.1021/acs.inorgchem.9b01529.  https://www.osti.gov/servlets/purl/1580967.

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@article{osti_1580967,

  title        = {Spectroscopic Characterization of $μ$-$η$1:$η$1-Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters},

  author       = {Palermo, Andrew P. and Schöttle, Christian and Zhang, Shengjie and Grosso-Giordano, Nicolás A. and Okrut, Alexander and Dixon, David A. and Frei, Heinz and Gates, Bruce C. and Katz, Alexander},

  abstractNote = {Although oxygen is a common ligand in supported metal catalysts, its coordination has been challenging to elucidate. Herein we characterize a diiridium complex that has been previously shown by X-ray diffraction crystallography to incorporate a μ-η1:η1-peroxo ligand. We observe markedly enhanced intensity at 788 cm-1 in the Raman spectrum of this complex, which is a consequence of bonding of the peroxo ligand but does not shift upon 18O labeling. Electronic structure calculations at the density functional theory level suggest that this increase in Raman intensity results from bands associated with rocking of CH2 substituents directly attached to P(Ph)2 groups coupling with the O-O band. These results provide part of the foundation for understanding oxygen ligands on a silica-supported tetrairidium carbonyl cluster stabilized with bulky electron-donating phosphine ligands [p-tert-butyl-calix[4]arene(OPr)3(OCH2PPh2) (Ph = phenyl; Pr = propyl)]. Reaction of the cluster with O2 also led to the growing in of a Raman band at 788 cm-1, similar to that in the diiridium complex and also assigned to the bonding of a bridging peroxo ligand. Infrared spectra recorded as the supported cluster reacted in sequential exposures to (i) H2, (ii) O2, (iii) H2, and (iv) CO indicate that two bridging peroxo ligands were bonded irreversibly per tetrairidium cluster, replacing bridging carbonyl ligands without altering either the cluster frame or the phosphine ligands. X-ray absorption near edge and infrared spectra include isosbestic points signifying a stoichiometrically simple reaction of the cluster with O2, and mass spectra of the effluent gas show that CO2 formed by oxidation of one terminal CO ligand per cluster as H2 (and not H2O) formed, evidence that hydride ligands had been present on the cluster following treatment (i). The understanding of how O2 reacts with the metal polyhedron provides a foundation for understanding of how oxidation catalysis may proceed on the surfaces of noble metals.},

  doi          = {10.1021/acs.inorgchem.9b01529},

  journal      = {Inorganic Chemistry},

  number       = 21,

  volume       = 58,

  place        = {United States},

  year         = {2019},

  month        = {10}

}

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https://doi.org/10.1021/acs.inorgchem.9b01529

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Figure 1: Top panel: Schematic representation of the sequence of gas treatments used to characterize the bonding of oxygen to the supported Ir₄ framework of 2. The horizontal arrows designate the gas to which the sample was exposed. The vertical arrows show the gases that were formed as products whenmore »

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Title: Spectroscopic Characterization of $$μ$$-$$η$$1:$$η$$1-Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters

Abstract

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Figures / Tables:

Title: Spectroscopic Characterization of $$μ$$-$$η$$¹:$$η$$¹-Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters