| |
[摘要]：[RhIIIH{(tBu2PCH2SiMe2NSiMe2CH2PtBu(CMe2CH2))}], ([RhH(PNP*)]), reacts with O2 in the time taken to mix the reagents to form a 1:1 h2-O2 adduct, for which O-O bond length is discussed with ref. to the reducing power of [RhH(PNP*)]. DFT calcns. faithfully replicate the obsd. O-O distance, and were used to understand the oxidn. state of this coordinated O2. The reactivity of [Rh(O2)(PNP)] towards H2, CO, N2, and O2 is tested and compared to the assocd. DFT reaction energies. Three different reagents effect single O atom transfer to [RhH(PNP*)]. The resulting [RhO(PNP)], characterized at ?-60?and by DFT calcns., is a ground-state triplet, is nonplanar, and reacts, e+15? with its own tBu C-H bond, to cleanly form a diamagnetic complex, [Rh(OH){N(SiMe2CH2PtBu2)(SiMe2CHPtBu{CMe2CH2})}]. |
|
