TY - JOUR
T1 - A comparative study of the electrochemical and proton-reduction behaviour of diphosphine-dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2)nS}] (M = Fe, Ru; n = 2, 3)
AU - Ghosh, Shishir
AU - Kabir, Shariff E.
AU - Hogarth, Graeme
PY - 2017/7/24
Y1 - 2017/7/24
N2 - The electrochemistry of dppm-bridged dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2)nS}] (M = Fe, Ru; n = 2, 3) has been studied by cyclic voltammetry. The diiron complexes show similar electrochemical responses in CH2Cl2 but differ significantly in MeCN, while the diruthenium complexes change only slightly with changes in the dithiolate backbone and solvent. Proton-reduction studies in MeCN with HBF4·Et2O as the proton source show that all are active catalysts for proton reduction in their singly reduced state. An additional catalytic event is observed for all, resulting from their partial protonation giving [M2(CO)4(μ-dppm){μ-S(CH2)nS}(μ-H)][BF4]. The diiron complexes show better long-term stability to acids, the diruthenium complexes degrading at high acid concentrations.
AB - The electrochemistry of dppm-bridged dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2)nS}] (M = Fe, Ru; n = 2, 3) has been studied by cyclic voltammetry. The diiron complexes show similar electrochemical responses in CH2Cl2 but differ significantly in MeCN, while the diruthenium complexes change only slightly with changes in the dithiolate backbone and solvent. Proton-reduction studies in MeCN with HBF4·Et2O as the proton source show that all are active catalysts for proton reduction in their singly reduced state. An additional catalytic event is observed for all, resulting from their partial protonation giving [M2(CO)4(μ-dppm){μ-S(CH2)nS}(μ-H)][BF4]. The diiron complexes show better long-term stability to acids, the diruthenium complexes degrading at high acid concentrations.
UR - http://www.scopus.com/inward/record.url?scp=85025648620&partnerID=8YFLogxK
U2 - 10.1007/s11243-017-0164-6
DO - 10.1007/s11243-017-0164-6
M3 - Article
AN - SCOPUS:85025648620
SN - 0340-4285
SP - 1
EP - 7
JO - Transition Metal Chemistry
JF - Transition Metal Chemistry
ER -