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Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety

  1. Alexander Y. Verat,
  2. Hongjun Fan,
  3. Maren Pink,
  4. Y.-S. Chen,
  5. Kenneth G. Caulton Prof.

Article first published online: 4 AUG 2008

DOI: 10.1002/chem.200800573

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 14, Issue 25, pages 7680–7686, August 28, 2008

Additional Information

How to Cite

Verat, Alexander Y., Fan, H., Pink, M., Chen, Y.-S. and Caulton, Kenneth G. (2008), Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety. Chem. Eur. J., 14: 7680–7686. doi: 10.1002/chem.200800573

Author Information

  1. Department of Chemistry, Indiana University, Bloomington, IN and Argonne National Laboratory, Argonne IL (USA), Fax: (+1) 812-855-8300

Publication History

  1. Issue published online: 25 AUG 2008
  2. Article first published online: 4 AUG 2008
  3. Manuscript Received: 27 MAR 2008

Funded by

  • National Science Foundation. Grant Numbers: NSF-CHE-0544829, CHE0087817
  • DOE-BES. Grant Number: W-31–109-Eng-38

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Keywords:

  • C[BOND]H activation;
  • dioxygen ligands;
  • nitrous oxide;
  • oxo ligands;
  • rhodium

Abstract

[RhIIIH{(tBu2PCH2SiMe2NSiMe2CH2PtBu{CMe2CH2})}], ([RhH(PNP*)]), reacts with O2 in the time taken to mix the reagents to form a 1:1 η2-O2 adduct, for which O[BOND]O bond length is discussed with reference to the reducing power of [RhH(PNP*)]; DFT calculations faithfully replicate the observed O–O distance, and are used to understand the oxidation state of this coordinated O2. The reactivity of [Rh(O2)(PNP)] towards H2, CO, N2, and O2 is tested and compared to the associated DFT reaction energies. Three different reagents effect single oxygen atom transfer to [RhH(PNP*)]. The resulting [RhO(PNP)], characterized at and above −60 °C and by DFT calculations, is a ground-state triplet, is nonplanar, and reacts, above about +15 °C, with its own tBu C[BOND]H bond, to cleanly form a diamagnetic complex, [Rh(OH){N(SiMe2CH2PtBu2)(SiMe2CH2PtBu{CMe2CH2})}].

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