Photochemical Pump and NMR Probe to monitor the formation and kinetics of hyperpolarized metal dihydrides

TY - JOUR

T1 - Photochemical Pump and NMR Probe to monitor the formation and kinetics of hyperpolarized metal dihydrides

AU - Procacci, Barbara

AU - Aguiar, Pedro M.

AU - Halse, Meghan Eileen

AU - Perutz, Robin Noel

AU - Duckett, Simon

N1 - © The Royal Society of Chemistry

PY - 2016/12/1

Y1 - 2016/12/1

N2 - On reaction of IrI(CO)(PPh 3) 21with para-hydrogen(p-H 2),Ir(H) 2I(CO)(PPh 3) 22 is formed which exhibits strongly enhanced 1H NMR signals for its hydride resonances. Complex 2 also shows similar enhancement of its NMR spectra when it is irradiated under p-H 2. We report the use of this photochemical reactivity to measure the kinetics of H 2 addition by laser-synchronized reactions in conjunction with NMR. The single laser pulse promotes the reductive elimination of H 2 from Ir(H) 2I(CO)(PPh 3) 22 in C 6D 6 solution to form the 16-electron precursor 1, back reaction with p-H 2 then reforms 2 in a well-defined nuclear spin-state. The build up of this product can be followed by incrementing a precisely controlled delay (τ), in millisecond steps, between the laser and the NMR pulse. The resulting signal vs. time profile shows a dependence on p-H 2 pressure. The plot of k obs against p-H 2 pressure is linear and yields the second order rate constant, k 2, for H 2 addition to 1 of (3.26 ± 0.42) × 10 2 M −1 s −1. Validation was achieved by transient-UV-vis absorption spectroscopy which gives k 2 of (3.06 ± 0.40) × 10 2 M −1 s −1. Furthermore, irradiation of a C 6D 6 solution of 2 with multiple laser shots, in conjunction with p-H 2 derived hyperpolarization, allows the detection and characterisation of two minor reaction products, 2a and 3, which are produced in such low yields that they are not detected without hyperpolarization. Complex 2a is a configurational isomer of 2, while 3 is formed by substitution of CO by PPh 3

AB - On reaction of IrI(CO)(PPh 3) 21with para-hydrogen(p-H 2),Ir(H) 2I(CO)(PPh 3) 22 is formed which exhibits strongly enhanced 1H NMR signals for its hydride resonances. Complex 2 also shows similar enhancement of its NMR spectra when it is irradiated under p-H 2. We report the use of this photochemical reactivity to measure the kinetics of H 2 addition by laser-synchronized reactions in conjunction with NMR. The single laser pulse promotes the reductive elimination of H 2 from Ir(H) 2I(CO)(PPh 3) 22 in C 6D 6 solution to form the 16-electron precursor 1, back reaction with p-H 2 then reforms 2 in a well-defined nuclear spin-state. The build up of this product can be followed by incrementing a precisely controlled delay (τ), in millisecond steps, between the laser and the NMR pulse. The resulting signal vs. time profile shows a dependence on p-H 2 pressure. The plot of k obs against p-H 2 pressure is linear and yields the second order rate constant, k 2, for H 2 addition to 1 of (3.26 ± 0.42) × 10 2 M −1 s −1. Validation was achieved by transient-UV-vis absorption spectroscopy which gives k 2 of (3.06 ± 0.40) × 10 2 M −1 s −1. Furthermore, irradiation of a C 6D 6 solution of 2 with multiple laser shots, in conjunction with p-H 2 derived hyperpolarization, allows the detection and characterisation of two minor reaction products, 2a and 3, which are produced in such low yields that they are not detected without hyperpolarization. Complex 2a is a configurational isomer of 2, while 3 is formed by substitution of CO by PPh 3

UR - http://www.scopus.com/inward/record.url?scp=84995560934&partnerID=8YFLogxK

U2 - 10.1039/C6SC01956K

DO - 10.1039/C6SC01956K

M3 - Article

SN - 2041-6520

VL - 7

SP - 7087

EP - 7093

JO - Chemical Science

JF - Chemical Science

IS - 12

M1 - SC-EDG-05-2016-001956.R1

ER -