期刊
INORGANIC CHEMISTRY
卷 47, 期 7, 页码 2261-2263出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic800030y
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资金
- NIGMS NIH HHS [R01 GM061153-06, R01 GM061153] Funding Source: Medline
Protonation of the symmetrical tetraphosphine complexes Fe-2(S2CnH2n)(CO)(2)(dppv)(2) afforded the corresponding terminal hydrides, establishing that even symmetrical diiron(l) dithiolates undergo protonation at terminal sites. The terminal hydride [HFe2(S2C3H6)(CO)(2)(dppv)(2)](+) was found to catalyze proton reduction at potentials 200 mV milder than the isomeric bridging hydride, thereby establishing a thermodynamic advantage for catalysis operating via terminal hydride. The azadithiolate protonates to afford, [Fe-2[(SCH2)(2)NH2YCO)(2)(dppv)(2)](+), [HFe2[(SCH2)(2)NH](CO)(2)-(dppv)(2)](+), and [HFe2[(SCH2)(2)NH2](CO)(2)(dppv)(2)](2+), depending on conditions.
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