Reversible Hyperpolarization of Ketoisocaproate Using Sulfoxide‐containing Polarization Transfer Catalysts

The substrate scope of sulfoxide-containing magnetisation transfer catalysts is extended to hyperpolarize α-ketoisocaproate and α-ketoisocaproate-1-[13 C]. This is achieved by forming [Ir(H)2 (κ2 -ketoisocaproate)(N-heterocyclic carbene)(sulfoxide)] which transfers latent magnetism from p-H2 via the signal amplification by reversible exchange (SABRE) process. The effect of polarization transfer field on the formation of enhanced 13 C magnetization is evaluated. Consequently, performing SABRE in a 0.5 μT field enabled most efficient magnetisation transfer. 13 C NMR signals for α-ketoisocaproate-1-[13 C] in methanol-d4 are up to 985-fold more intense than their traditional Boltzmann derived signal intensity (0.8 % 13 C polarisation). Single crystal X-ray diffraction reveals the formation of the novel catalyst decomposition products [Ir(μ-H)(H)2 (IMes)(SO(Ph)(Me)2 )]2 and [(Ir(H)2 (IMes)(SO(Me)2 ))2 (μ-S)] when the sulfoxides methylphenylsulfoxide and dimethylsulfoxide are used respectively.