Mechanistic Insight into Novel Sulfoxide Containing SABRE Polarisation Transfer Catalysts

TY - JOUR

T1 - Mechanistic Insight into Novel Sulfoxide Containing SABRE Polarisation Transfer Catalysts

AU - Tickner, Benjamin James

AU - Lewis, Jennifer Sunari

AU - John, Richard Owain

AU - Whitwood, Adrian C.

AU - Duckett, Simon

N1 - © The Royal Society of Chemistry 2019

PY - 2019/9/24

Y1 - 2019/9/24

N2 - Signal Amplification By Reversible Exchange (SABRE) is a hyperpolarisation technique that commonly uses [Ir(H)2(carbene)(substrate)3]Cl complexes to catalytically transfer magnetisation from para-hydrogen derived hydride ligands to coordinated substrates. Here, we explore the reactivity of a novel class of such catalysts based on sulfoxide containing [IrCl(H)2(carbene)(DMSO)2], which are involved in the hyperpolarisation of pyruvate using SABRE. We probe the reactivity of this species by NMR and DFT and upon reaction with sodium pyruvate establish the formation of two isomers of [Ir(H)2(η2-pyruvate)(DMSO)(IMes)]. Studies with related disodium oxalate yield [Ir2(H)4(IMes)2(DMSO)2(κ2-η2-Oxalate)] that is characterised by NMR and X-ray diffraction.

AB - Signal Amplification By Reversible Exchange (SABRE) is a hyperpolarisation technique that commonly uses [Ir(H)2(carbene)(substrate)3]Cl complexes to catalytically transfer magnetisation from para-hydrogen derived hydride ligands to coordinated substrates. Here, we explore the reactivity of a novel class of such catalysts based on sulfoxide containing [IrCl(H)2(carbene)(DMSO)2], which are involved in the hyperpolarisation of pyruvate using SABRE. We probe the reactivity of this species by NMR and DFT and upon reaction with sodium pyruvate establish the formation of two isomers of [Ir(H)2(η2-pyruvate)(DMSO)(IMes)]. Studies with related disodium oxalate yield [Ir2(H)4(IMes)2(DMSO)2(κ2-η2-Oxalate)] that is characterised by NMR and X-ray diffraction.

U2 - 10.1039/c9dt02951f

DO - 10.1039/c9dt02951f

M3 - Article

SN - 1477-9234

JO - Dalton Transactions

JF - Dalton Transactions

ER -