Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety
- UC
[Rh{sup III}H{l_brace}(tBu{sub 2}PCH{sub 2}SiMe{sub 2}NSiMe{sub 2}CH{sub 2}PtBu{l_brace}CMe{sub 2}CH{sub 2}{r_brace}){r_brace}], ([RhH(PNP*)]), reacts with O{sub 2} in the time taken to mix the reagents to form a 1:1 {eta}{sub 2}-O{sub 2} adduct, for which O-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 O{sub 2}. The reactivity of [Rh(O{sub 2})(PNP)] towards H{sub 2}, CO, N{sub 2}, and O{sub 2} 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 CH bond, to cleanly form a diamagnetic complex, [Rh(OH){l_brace}N(SiMe{sub 2}CH{sub 2}PtBu{sub 2})(SiMe{sub 2}CH{sub 2}PtBu{l_brace}CMe{sub 2}CH{sub 2}{r_brace}){r_brace}].
- Research Organization:
- Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)
- Sponsoring Organization:
- NSFDOE - BASIC ENERGY SCIENCES
- OSTI ID:
- 1031342
- Journal Information:
- Chemistry, Journal Name: Chemistry Journal Issue: 25 Vol. 14; ISSN 0947-6539; ISSN CEUJED
- Country of Publication:
- United States
- Language:
- ENGLISH
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