ABSTRACT
The short lived pincer complex [(C5H3N(CH2P((t)Bu)2)2)Ir(H)2(py)]BF4 is shown to be active for signal amplification by reversible exchange. This catalyst formulation enables the efficient transfer of polarization from parahydrogen to be placed into just a single molecule of the hyperpolarisation target, pyridine. When the catalysts (1)H nuclei are replaced by (2)H, increased levels of substrate hyperpolarization result and when the reverse situation is examined the catalyst itself is clearly visible through hyperpolarised signals. The ligand exchange pathways of [(C5H3N(CH2P((t)Bu)2)2)Ir(H)2(py)]BF4 that are associated with this process are shown to involve the formation of 16-electron [(C5H3N(CH2P((t)Bu)2)2)Ir(H)2]BF4 and the 18-electron H2 addition product [(C5H3N(CH2P((t)Bu)2)2)Ir(H)2(H2)]BF4.
Subject(s)
Coordination Complexes/chemistry , Iridium/chemistry , Coordination Complexes/chemical synthesis , Crystallography, X-Ray , Hydrogen/chemistry , Magnetic Resonance Spectroscopy , Molecular Conformation , Pyridines/chemistryABSTRACT
Aromatic hydrogenation is a challenging transformation typically requiring alkali or transition metal reagents and/or harsh conditions to facilitate the process. In sharp contrast, the aromatic heterocycle 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene is shown to be reduced under 4 atm of H2 to give [3.1.0]bicylo reduction products, with the structure of the major isomer being confirmed by X-ray crystallography. NMR studies show this reaction proceeds via a reversible 1,4-H2 addition to generate an intermediate species, which undergoes an irreversible suprafacial hydride shift concurrent with P-P bond formation to give the isolated products. Further, para-hydrogen experiments confirmed the addition of H2 to triphosphabenzene is a bimolecular process. Density functional theory (DFT) calculations show that facile distortion of the planar triphosphabenzene toward a boat-conformation provides a suprafacial combination of vacant acceptor and donor orbitals that permits this direct and uncatalyzed reduction of the aromatic molecule.