Electronic Effects of (N2S2)M(NO) Complexes (M = Fe, Co) as Metallodithiolate Ligands.

Electronic Effects of (N2S2)M(NO) Complexes (M = Fe, Co) as Metallodithiolate Ligands. Research Abstract Details 

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Electronic Effects of (N2S2)M(NO) Complexes (M = Fe, Co) as Metallodithiolate Ligands. Abstract Text:

Heterobimetallic complexes comprised of W(CO) 4 adducts of (N 2S 2)M(NO) have been isolated and characterized by nu(CO) and nu(NO) IR spectroscopies and X-ray diffraction. The molecular structures of (N 2S 2)M(NO) compounds (bme-dach)Co(NO), [(bme-dach)Co(NO)]W(CO) 4, and [(bme-dach)Fe(NO)]W(CO) 4 [bme-dach = N, N'-bis(2-mercaptoethyl)-1,4-diazacycloheptane)] find the square-pyramidal (bme-dach)M(NO) unit to serve as a bidentate ligand via the cis-dithiolato sulfurs, with a hinge angle of the butterfly bimetallic structures of ca. 130 degrees . The W(CO) 4 moiety is used as a probe of the electron-donor ability of the nitrosyl complexes through CO stretching frequencies that display a minor increase as compared to analogous [(N 2S 2)Ni]W(CO) 4 complexes. These findings are consistent with the electron-withdrawing influence of the {Co(NO)} (8) and {Fe(NO)} (7) units on the bridging thiolate sulfurs relative to Ni (2+). Also sensitive to derivatization by W(CO) 4 is the NO stretch, which blue shifts by ca. 30 and 50 cm (-1) for the Co and Fe complexes, respectively. Cyclic voltammetry studies find similar reduction potentials (-1.08 V vs NHE in N, N-dimethylformamide solvent) of the (bme-dach)Co(NO) and (bme-dach)Fe(NO) free metalloligands, which are positively shifted by ca. 0.61 and 0.48 V, respectively, upon complexation to W(CO) 4.

Electronic Effects of (N2S2)M(NO) Complexes (M = Fe, Co) as Metallodithiolate Ligands. Publishing Authors By Initials

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Electronic Effects of (N2S2)M(NO) Complexes (M = Fe, Co) as Metallodithiolate Ligands. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Inorganic chemistry

VOLUME: 47

Page Numbers: 2056-63

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ISSN: 0020-1669

DAY: 9

MONTH: 02

YEAR: 2008

Electronic Effects of (N2S2)M(NO) Complexes (M = Fe, Co) as Metallodithiolate Ligands. Information

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LANGUAGE: eng

NlmUniqueID: 366543

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AFFILIATION: marcetta@mail.chem.tamu.edu.

Country: United States

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MEDLINETA: Inorg Chem

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