A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO)₃Fe(μ-StBu)₃Ni{SC₆H₃-2,6-(mesityl)₂} and reversible CO addition at the Ni site
2010
Ohki, Yasuhiro | Yasumura, Kazunari | Andō, Masaru | Shimokata, Satoko | Tatsumi, Kazuyuki
A [NiFe] hydrogenase model compound having a distorted trigonal-pyramidal nickel center, (CO)₃Fe(μ-StBu)₃Ni(SDmp), 1 (Dmp = C₆H₃-2,6-(mesityl)₂), was synthesized from the reaction of the tetranuclear Fe-Ni-Ni-Fe complex [(CO)₃Fe(μ-StBu)₃Ni]₂(μ-Br)₂, 2 with NaSDmp at -40 °C. The nickel site of complex 1 was found to add CO or CNtBu at -40 °C to give (CO)₃Fe(StBu)(μ-StBu)₂Ni(CO)(SDmp), 3, or (CO)₃Fe(StBu)(μ-StBu)₂Ni(CNtBu)(SDmp), 4, respectively. One of the CO bands of 3, appearing at 2055 cm⁻¹ in the infrared spectrum, was assigned as the Ni-CO band, and this frequency is comparable to those observed for the CO-inhibited forms of [NiFe] hydrogenase. Like the CO-inhibited forms of [NiFe] hydrogenase, the coordination of CO at the nickel site of 1 is reversible, while the CNtBu adduct 4 is more robust.
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