title: Spin state, structure, and reactivity of terminal oxo and dioxygen complexes of the (PNP)Rh moiety.
abstract: [Rh(III)H{(tBu(2)PCH(2)SiMe(2)NSiMe(2)CH(2)PtBu{CMe(2)CH(2)})}], ([RhH(PNP*)]), reacts with O(2) in the time taken to mix the reagents to form a 1:1 eta(2)-O(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(2). The reactivity of [Rh(O(2))(PNP)] towards H(2), CO, N(2), and O(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 degrees C and by DFT calculations, is a ground-state triplet, is nonplanar, and reacts, above about +15 degrees C, with its own tBu C--H bond, to cleanly form a diamagnetic complex, [Rh(OH){N(SiMe(2)CH(2)PtBu(2))(SiMe(2)CH(2)PtBu{CMe(2)CH(2)})}].
authors.affiliation: Department of Chemistry, Indiana University, Bloomington, IN, USA.
authors.forename: Alexander Y
authors.initials: AY
authors.lastname: Verat
authors.forename: Hongjun
authors.initials: H
authors.lastname: Fan
authors.forename: Maren
authors.initials: M
authors.lastname: Pink
authors.forename: Y-S
authors.initials: YS
authors.lastname: Chen
authors.forename: Kenneth G
authors.initials: KG
authors.lastname: Caulton
mesh_terms: D018360:Crystallography, X-Ray; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D012238:Rhodium; D010100:Oxygen