Chemical evolution of a nitrogenase model. X. Reduction of coordinated cyanide ion in cyano complexes of molybdenum(IV) and their use as catalysts for the reduction of molecular nitrogen and of other substrates

Journal Article · Wed Nov 26 04:00:00 EST 1975 · J. Am. Chem. Soc., v. 97, no. 24, pp. 7069-7076

DOI:https://doi.org/10.1021/ja00857a018· OSTI ID:4130101

Schrauzer, G M; Robinson, P R; Moorehead, E L; Vickrey, T M

The complex anions [Mo(O)$sub 2$(CN)$sub 4$$]$$sup 4-$ (1), [MO(O)(OH)(CN)$sub 4$$]$$sup 3-$ (2), and [Mo(O)(H$sub 2$O)(CN)$sub 4$$]$$sup 2-$ (3) represent rare examples of defined monomeric complexes of oxomolybdate(IV) and may be regarded as models of substrate-catalyst complexes in the reduction of CN$sup -$ by molybdothiol catalyst systems. The reduction of coordinated CN$sup - $ in 3 to NH$sub 3$, CH$sub 4$, C$sub 2$$H$$sub 6$, and C$sub 2$$H$$sub 4$ was demonstrated with BH$sub 4$$sup -$, S$sub 2$$O$$sub 4$$sup 2-$, and reduced ferredoxin model compounds as reducing agents. Evidence for a significant stimulatory effect of adenosine triphosphate (ATP) was also obtained. The reduction of coordinated CN$sup -$ is inhibited by O$sub 2$, CO, and the known substrates of nitrogenase enzymes. The latter are reduced under the reaction conditions, involving coordinatively unsaturated cyano complexes of oxomolybdate(IV) as the catalysts. The reduction of molecular N$sub 2$ to NH$sub 3$ and traces of N$sub 2$$H$$sub 4$ was also observed and proceeds more efficiently than in the molybdothiol model systems of nitrogenase. ATP causes a significant stimulation of CN$sup -$ reduction in H$sub 2$O, but not in D$sub 2$O. (auth)

• Research Organization: Univ. of California, San Diego
• Sponsoring Organization: USDOE
• NSA Number: NSA-33-014281
• OSTI ID: 4130101
• Journal Information: J. Am. Chem. Soc., v. 97, no. 24, pp. 7069-7076, Journal Name: J. Am. Chem. Soc., v. 97, no. 24, pp. 7069-7076; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

*DEUTERIUM-- ISOTOPE EFFECTS
400202* --Chemistry--Inorganic & Physical Chemistry--Isotope Effects
CATALYSTS
CYANIDES
HEAVY WATER
MOLYBDENUM COMPLEXES
N40220* --Chemistry--Inorganic
Organic
& Physical Chemistry--Isotopic Effects
NITROGEN
REDUCTION
WATER