Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation.

Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation. Research Abstract Details 

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Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation. Abstract Text:

Russell P Pesavento,Curtis P Berlinguette,R H Holm,

Recent work has shown that cyanide ligation increases the redox potentials of Fe(4)S(4) clusters, enabling the isolation of [Fe(4)S(4)(CN)4]4-, the first synthetic Fe(4)S(4) cluster obtained in the all-ferrous oxidation state (Scott, T. A.; Berlinguette, C. P.; Holm, R. H.; Zhou, H.-C. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 9741). The generality of reduced cluster stabilization has been examined with MoFe(3)S(4) clusters. Reaction of single-cubane [(Tp)MoFe(3)S(4)(PEt(3))3]1+ and edge-bridged double-cubane [(Tp)2Mo(2)Fe(6)S(8)(PEt(3))4] with cyanide in acetonitrile affords [(Tp)MoFe(3)S(4)(CN)3]2- (2) and [(Tp)2Mo(2)Fe(6)S(8)(CN)4]4- (5), respectively. Reduction of 2 with KC(14)H(10) yields [(Tp)MoFe(3)S(4)(CN)3]3- (3). Clusters were isolated in approximately 70-90% yields as Et(4)N+ or Bu(4)N+ salts; clusters 3 and 5 contain all-ferrous cores, and 3 is the first [MoFe(3)S(4)]1+ cluster isolated in substance. The structures of 2 and 3 are very similar; the volume of the reduced cluster core is slightly larger (2.5%), a usual effect upon reduction of cubane-type Fe(4)S(4) and MFe(3)S(4) clusters. Redox potentials and 57Fe isomer shifts of [(Tp)MoFe(3)S(4)L3]2-,3- and [(Tp)2Mo(2)Fe(6)S(8)L(4)]4-,3- clusters with L = CN-, PhS-, halide, and PEt3 are compared. Clusters with pi-donor ligands (L = halide, PhS) exhibit larger isomer shifts and lower (more negative) redox potentials, while pi-acceptor ligands (L = CN, PEt3) induce smaller isomer shifts and higher (less-negative) redox potentials. When the potentials of 3/2 and [(Tp)MoFe(3)S(4)(SPh)3]3-/2- are compared, cyanide stabilizes 3 by 270 mV versus the reduced thiolate cluster, commensurate with the 310 mV stabilization of [Fe(4)S(4)(CN)4]4- versus [Fe(4)S(4)(SPh)4]4- where four ligands differ. These results demonstrate the efficacy of cyanide stabilization of lower cluster oxidation states. (Tp = hydrotris(pyrazolyl)borate(1-)).

Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation. Publishing Authors By Initials

RP Pesavento,CP Berlinguette,RH Holm,

For similar investigative techniques: chemistry, analytical: crystallography: x-ray diffraction research abstracts see: investigative techniques: chemistry, analytical: crystallography: x-ray diffraction research

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Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation. Journal Published:

PUBLICATION TYPE: Research Support, N.I.H., Extr

Journal: Inorganic chemistry

VOLUME: 46

Page Numbers: 510-6

Journal Abbreviation:

ISSN: 0020-1669

DAY: 22

MONTH: Jan

YEAR: 2007

Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation. Information

Number of References:

LANGUAGE: eng

NlmUniqueID: 366543

Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation. Keywords Mesh Terms:

KEYWORDS: X-Ray Diffraction

MESH TERMS: chemistry

Chemical & Substance for Abstract: Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation. Information

Substance Name: Sulfur

Registry Number: 7704-34-9

Grant and Affiliation Information for Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation.

AFFILIATION: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM 28856

ACRONYM: GM

MEDLINETA: Inorg Chem

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