Isolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O–O bond

The reaction of RhCl3·H2O with tBu2P(CH2)5PtBu2 afforded several complexes including [RhIII(H)Cl{tBu2P(CH2)2CH(CH2)2PtBu2}] (1), [RhIIIHCl2{tBu2P(CH2)5PtBu2}]2 (2), [RhICl{tBu2P(CH2)2CHCHCH2PtBu2}] (3) and [RhICl{tBu2PCH2C(O)CHCHCH2PtBu2}] (4). X-ray crystal structures of 3 and 4 showed that the CC bond on the C5 unit of tBu2P(CH2)5PtBu2 is bound to Rh(I) in a η2 configuration. In 4, the Rh atom has a trigonal pyramidal coordination geometry. The X-ray crystal structure of 2 consists of two rhodium(III) centers bridged by two tBu2P(CH2)5PtBu2 ligands with two phosphorus atoms, one from each ligand, trans to one another. The crystal structure of the rhodium oxygen adduct with 1,3-bis(di-t-butylphosphinomethyl)benzene [RhO2{tBu2PCH2(C6H3)CH2PtBu2}] (5) was also investigated. In this species the O2 is η2 coordinated to the Rh(I) center with asymmetric Rh–O bond lengths (2.087(7) and 1.998(8) Å). The O–O bond distance is short (1.337(11) Å) with νO–O of 990.5 cm−1. DFT calculations on complex 5 yielded two η2–O2 structures that differed in energy by only 0.76 kcal/mol. The lower energy one (5a) had near C2 symmetry, and had nearly equal Rh–O bond lengths, while the higher energy structure (5b) had near Cs symmetry and generally good agreement with the experimental structure. The calculated UV–Vis and IR spectra of complex 5 are in excellent agreement with experiment.

X-ray structures of four Rh(PCP) complexes have been determined.The Rh(PCP)O2 complex has a short O–O bond distance (1.337 Å) with νO–O of 990.5 cm−1.DFT calculations on Rh(PCP)O2 yielded two η2–O2 structures that differed in energy by only 0.76 kcal/mol.Figure optionsDownload as PowerPoint slide