Redox behavior of the black roussinate heptanitrosyltrisulfotetraferrate(1-) monoanion. Synthesis and spectroscopic characterization of the [Fe4S3(NO)7]n- (n = 2, 3) anions and crystal structures of the mono- and dianions in their [NEt4]+ salts

D'Addario, Sabatino; Demartin, Francesco; Grossi, Loris; Iapalucci, Maria Carmela; Laschi, Franco; Longoni, Giuliano; Zanello, Piero

doi:10.1021/ic00059a022

Cited by 46 publications

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“…62,63,64 The reduced form of this complex, [Fe 4 (NO) 4 (μ 3 -S) 4 ] − , was also studied 64. The tetranuclear [Fe 4 (NO) 7 (μ 3 -S) 3 ] − species (Scheme 1G), known as Roussin’s black salt (RBS),63,65,66 was not included in the isomer shift fit but was chosen instead as a test of the fitted parameters.…”

Section: Resultsmentioning

confidence: 99%

Density Functional Theory Calculations on Mössbauer Parameters of Nonheme Iron Nitrosyls

2009

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DFT calculations on transition metal nitrosyls often reveal unusual spin density profiles, involving substantial spatial separation of majority and minority spin densities. Against this context, there is a significant lack of studies where DFT calculations have been quantitatively calibrated against experimental spectroscopic properties. Reported herein are DFT calculations of Mössbauer isomer shifts and quadrupole splittings for 21 nonheme iron complexes (26 distinct iron sites) including 9 iron nitrosyls. Low-(S = 1/2) and high-spin (S = 3/2) {FeNO} 7 complexes, S = 1/2 {Fe(NO) 2 } 9 species, and polynuclear iron nitrosyls are all represented within the set of compounds examined. The general conclusion with respect to isomer shifts is that DFT (OLYP/STO-TZP) performs comparably well for iron nitrosyls and for iron complexes in general. However, quadrupole splittings are less accurately reproduced for nitrosyl complexes.

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Section: Resultsmentioning

confidence: 99%

Density Functional Theory Calculations on Mössbauer Parameters of Nonheme Iron Nitrosyls

2009

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“…Structures closely resemble that of the classic Roussin’s black anion, [Fe 4 S 3 (NO) 7 ] 1− , which is prepared by self-assembly. 78 The weak-field Fe 4 S 3 core is proposed as an intermediate in the formation of an Fe 8 S 7 cluster from two [Fe 4 S 4 {N(SiMe 3 ) 2 } 4 ] clusters and PR 3 . 79 As yet, no synthetic weak field Fe 4 S 3 cluster has been isolated, although it seems highly probable that establishment of the proximal cluster will encourage research toward that end.…”

Section: Fe4s4 Clustersmentioning

confidence: 99%

Developments in the Biomimetic Chemistry of Cubane-Type and Higher Nuclearity Iron–Sulfur Clusters

Lo²,

2014

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“…An iron nitrosyl complex with structural parameters and ν NO values similar to those in 6 is the Roussin black salt (RBS), (Et 4 N)[Fe 4 S 3 (NO) 7 ] (VId). 80 The greater average N-O distance in VId compared to 6, the more acute average M-N-O angle and more obtuse S-M-S angle in VId, and the lower ν NO values suggest that there is greater M-NO π-backbonding in VId than in 6. Although 6 contains three {Co(NO) 2 } 10 units and VId three equatorial {Fe(NO) 2 } 9 units, the latter are bridged by sulfides and the complex is overall anionic, thus providing a more electron-rich environment for the metal centers in VId.…”

Section: Synthesis and Properties Of The First Mononuclear {Co(no) 2 mentioning

confidence: 98%

Synthesis and Characterization of {Ni(NO)}¹⁰ and {Co(NO)₂}¹⁰ Complexes Supported by Thiolate Ligands

2008

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Nitric oxide is an important molecule in biology and modulates a variety of physiological and pathophysiological processes. Some of its regulatory functions are exerted through interactions with redox-active elements, including iron, nickel, cobalt, and sulfur. Metalloenzymes containing [ nFe- nS] ( n = 2 or 4) clusters can be activated or inactivated by reaction with NO, affording dinitrosyl iron complexes. Studies of the NO chemistry of small-molecule iron thiolate complexes have provided insight into these biological processes and suggested probable intermediates. To explore this chemistry from a different perspective, we prepared nickel and cobalt thiolate complexes and investigated their reactions with NO and related compounds. We report here the first examples of anionic complexes containing {Ni(NO)} (10) and {Co(NO) 2} (10) units, the reactivity of which suggests possible intermediates in the interconversion of iron thiolate nitrosyl compounds. Our results demonstrate new chemistry involving NO and simple complexes of nickel and cobalt supported by thiolates, which have been known for more than 30 years. The use of mass balance methodology was key to their discovery. Among the novel complexes reported are (Et 4N) 2[Ni(NO)(SPh) 3] ( 2), from (Et 4N) 2[Ni(SPh) 4] ( 1) and NO, (Et 4N) 2[Ni 2(NO) 2(mu-SPh) 2(SPh) 2] ( 3), from 1 and NO (+) or 2 and Me 3O (+), (Et 4N)[Co(NO) 2(SPh) 2] ( 5), from (Et 4N) 2[Co(SPh) 4] ( 4) and NO, and [Co 3(NO) 6(mu-SPh) 3] ( 6), from 5 and Me 3O (+). In the syntheses of 2 and 5, NO could be replaced by the convenient solid Ph 3CSNO.

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Redox behavior of the black roussinate heptanitrosyltrisulfotetraferrate(1-) monoanion. Synthesis and spectroscopic characterization of the [Fe4S3(NO)7]n- (n = 2, 3) anions and crystal structures of the mono- and dianions in their [NEt4]+ salts

Cited by 46 publications

References 0 publications

Density Functional Theory Calculations on Mössbauer Parameters of Nonheme Iron Nitrosyls

Density Functional Theory Calculations on Mössbauer Parameters of Nonheme Iron Nitrosyls

Developments in the Biomimetic Chemistry of Cubane-Type and Higher Nuclearity Iron–Sulfur Clusters

Synthesis and Characterization of {Ni(NO)}¹⁰ and {Co(NO)₂}¹⁰ Complexes Supported by Thiolate Ligands

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Redox behavior of the black roussinate heptanitrosyltrisulfotetraferrate(1-) monoanion. Synthesis and spectroscopic characterization of the [Fe4S3(NO)7]n- (n = 2, 3) anions and crystal structures of the mono- and dianions in their [NEt4]+ salts

Cited by 46 publications

References 0 publications

Density Functional Theory Calculations on Mössbauer Parameters of Nonheme Iron Nitrosyls

Density Functional Theory Calculations on Mössbauer Parameters of Nonheme Iron Nitrosyls

Developments in the Biomimetic Chemistry of Cubane-Type and Higher Nuclearity Iron–Sulfur Clusters

Synthesis and Characterization of {Ni(NO)}10 and {Co(NO)2}10 Complexes Supported by Thiolate Ligands

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Synthesis and Characterization of {Ni(NO)}¹⁰ and {Co(NO)₂}¹⁰ Complexes Supported by Thiolate Ligands