RESUMO
Spin hyperpolarization generated upon activation of parahydrogen, the spin-0 isomer of H2, by ansa-aminoboranes (AABs) constitutes a rare but interesting example of applied metal-free catalysis in parahydrogen-induced polarization (PHIP). AAB molecular moieties made of light elements would be useful in important areas of NMR, such as chemosensing and the production of hyperpolarized substances, or generally in NMR sensitivity enhancement. At the same time, little is known about the detailed mechanistic aspects of underlying chemical processes. Herein, we present a joint experimental-computational study of the kinetic and thermodynamic aspects of H2 activation by AABs, for the first time providing molecular-level details and results of PHIP experiments with AABs in various solvents. Specifically, a large number of kinetic and thermodynamic parameters are measured experimentally for H2 activation by 2-aminophenylboranes of variable steric bulkiness of the boryl site. A clear correlation between the experimental and DFT-predicted thermochemical parameters is observed. PHIP effects in toluene, dichloromethane, and acetonitrile are characterized and rationalized based on the use of the kinetic and nuclear spin relaxation parameters. Altogether, the obtained results provide valuable information for the further rational design of efficient AAB catalysts for metal-free PHIP based on frustrated Lewis pair (FLP) chemistry.