The Chemistry of Iron Carbonyl Sulfide and Selenide Anions

Holliday, Russell L.; Roof, Lisa C.; Hargus, Beverly; Smith, Donna M.; Wood, Paul T.; Pennington, William T.; Kolis, Joseph W.

doi:10.1021/ic00121a018

Cited by 52 publications

(35 citation statements)

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“…al. [21] In the reported struc- [(RS)Fe(CO) 3 ] 2 complex [19] if one includes the central NiS 4 unit as a chelating dithiolene group. In [Ni(dsdm){Fe(CO) 3 } 2 ] the sulfur-sulfur distance in the dithiolate group formed by the tetrahedral Ni(dsdm) unit is too large (4.13 Å ) for each sulfur to bind both Fe atoms; thus a FeSC 3 chromophore rather than the typical FeS 2 C 3 chromophore is observed.…”

Section: Resultsmentioning

confidence: 99%

Structure and Electronic Properties of [Ni(dsdm){Fe(CO)₃}₂], an Unusual, Triangular Nickel Diiron Compound

et al. 2003

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Reaction of the low-spin complex [Ni(dsdm)] with Fe 2 CO 9 results in the unique trinuclear cluster [Ni(dsdm){Fe(CO) 3 } 2 ]. NMR spectroscopy shows that the structure is diamagnetic, and, moreover, that the complex is stable in solution and C 2 -symmetric. The X-ray structure reveals short distances between the distorted octahedral nickel(II) ion and the two octahedral iron(0) centers. The observed diamagnetism is exIn recent years the discovery of organometallic-like fragments in the active sites of hydrogenase enzymes has given a new impetus to research pertaining to iron carbonyl chemistry. The active site of the enzyme extracted from D. gigas has been described as a heterodimetallic nickel-iron cluster in a sulfur-rich environment containing small diatomic CO or CN molecules coordinated to iron, [1] and the structure of the active site in the Fe-only hydrogenase isolated from D. desulfuricans comprises a diiron subcluster also containing CO and CN ligands.[2] Although few model compounds that properly match the active-site structure of [NiFe] hydrogenases have been reported, some do show various features of the metal coordination environment. [3Ϫ6] In spite of the research both in organometallic chemistry and in bioinorganic chemistry, the number of compounds containing both Ni and Fe bridged by a sulfur donor is rather limited. [7] Of bioinorganic interest among these are the Fe 3 Ni cubane clusters and Fe 4 S 4 clusters bridged to mononuclear nickel complexes, both cluster types being relevant to the active site in acetyl coenzyme-A synthase, [8,9] as well as a few heterodinuclear complexes relevant to the hydrogenase active site. [10] In the field of organometallic cluster chemistry a huge number of structures containing the (µ-S)-Fe 2 CO 6 fragment [a] have been reported. [11] This Fe 2 CO 6 fragment has recently gained renewed attention because of its importance in modeling the active site of Fe-only hydrogenases.[12] Research efforts by organometallic chemists have resulted in several complexes with a cyclopentadienylnickel unit bound to Fe(CO) 3 moieties. [13,14] The mononuclear compound [Ni(dsdm)] {H 2 dsdm ϭ [N,NЈ-dimethyl-N,NЈ-bis(2-sulfanylethyl)ethylenediamine]} is a nickel thiolate complex used in biomimetic studies of [NiFe] hydrogenases. [15] [Ni(dsdm)] contains two cis sulfur atoms which are particularly reactive towards dioxygen. Indeed, the oxidation of [Ni(dsdm)] with H 2 O 2 or O 2 leads to the fully oxidized [Ni(dsodm)(H 2 O) 2 ] complex in which nickel is coordinated to the sulfonato groups. [16,17] Moreover, [Ni(dsdm)] has also been used in attempts to synthesize thiolato-bridged nickel-iron complexes. The reaction of [Ni(dsdm)] with K[HFe(CO) 4 ] leads to [Fe(dsdm)Ni(CO) 3 ] 2 and involves the reduction of nickel() to nickel(0) followed by the coordination of the dsdm ligand to the iron(). [18] We present herein the reaction of [Ni(dsdm)] with Fe 2 CO 9 , which results in the formation of the novel trinuclear sulfur-bridged nickel-iron complex [Ni(dsdm){Fe(CO) 3 } 2 ], a di...

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Section: Resultsmentioning

confidence: 99%

Structure and Electronic Properties of [Ni(dsdm){Fe(CO)₃}₂], an Unusual, Triangular Nickel Diiron Compound

et al. 2003

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“…± NMR: Bruker AC 200 ( 1 H 200 Mhz, 13 5 were purchased from Aldrich and used as received. Fe 3 (CO) 12 , Ru 3 (CO) 12 and cpFe(CO) 2 Cl were prepared according to literature methods [15,16,17].…”

Section: Methodsmentioning

confidence: 99%

(Carbonyl)Iron-Selenolates: New Synthetic Methods and Reactions with Electrophiles. Crystal Structures of [(CO)6Fe2(μ-SeR)2]; R = Me3SiCH2 andp-O2NC6H4CH2, {(CO)6Fe2[μ-η2-Se,Se′-o-(SeCH2C6H4CH2Se)]}, and [(CO)6Fe2(μ-SeFe(CO)2cp)2]

Jäger

Jones

Laube

et al. 1999

Z. anorg. allg. Chem.

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The reactions of Fe(CO)5 or Fe3(CO)12 with NaBEt3H or KB[CH(CH3)C2H5]3H, respectively and treatment of the resulting carbonylates M2Fe(CO)4, M = Na, K with elemental selenium in appropriate ratios lead to the formation of M2[Fe2(CO)6(μ‐Se)2]. Subsequent reactions with organo halides or the complex fragment cpFe(CO)2+, cp = η5‐C5H5 afforded the selenolato complexes [Fe2(CO)6(μ‐SeR)2], R = CH2SiMe3 (1), CH2Ph (2), p‐CH2C6H4NO2 (3), o‐CH2C6H4CH2 (4) and cpFe(CO)2+ (5) in moderate to good yields. A similar reaction employing Ru3(CO)12, Se and p‐O2NC6H4CH2Br leads to the formation of the corresponding organic diselenide. The X‐ray structures of 1, 3, 4 and 5 were determined and revealed butterfly structures of the Fe2Se2 cores. The substituents in 1, 3 and 5 adopt different conformations depending on their steric demand. In 4, the conformation is fixed because of the chelate effect of the ligand. The Fe–Se bond lengths lie in the range 235 to 240 pm, with corresponding Fe–Fe bond lengths of 254 to 256 pm. The 77Se NMR data of the new complexes are discussed and compared with the corresponding data of related complexes.

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“…Dark brown Fe 4 Ni cluster [31] contains well-separated [PPh 4 ] 2+ cations, [(OC) 6 Fe 2^3 -S) 2 Fe 3 (CO) 6 ] 2~ anion and a CH 2 C1 2 molecule. The structure of the dianion consists of a distorted square planar nickel(II) center chelated by two Fe 2 (CO) 6 S 2 butterflies.…”

Section: Introductionmentioning

confidence: 99%

“…The shortest Fe-Fe bonds in the series of Fe 4 M clusters are: 2.500(1 )A (where M is a non-transition element (Te) [12]), 2.503(3)A (where M is a transition element (Ni) [31]), and 2.544(5)A (for the actinide element (U) [37].…”

Section: Introductionmentioning

confidence: 99%

Crystallographic and Structural Analysis of Iron Heterometallic Compounds Part IV: Heteropentameric Compounds

Melnı́k¹,

Ondrejkovičová²,

Koman³

2010

Reviews in Inorganic Chemistry

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The Chemistry of Iron Carbonyl Sulfide and Selenide Anions

Cited by 52 publications

References 1 publication

Structure and Electronic Properties of [Ni(dsdm){Fe(CO)₃}₂], an Unusual, Triangular Nickel Diiron Compound

Structure and Electronic Properties of [Ni(dsdm){Fe(CO)₃}₂], an Unusual, Triangular Nickel Diiron Compound

(Carbonyl)Iron-Selenolates: New Synthetic Methods and Reactions with Electrophiles. Crystal Structures of [(CO)6Fe2(μ-SeR)2]; R = Me3SiCH2 andp-O2NC6H4CH2, {(CO)6Fe2[μ-η2-Se,Se′-o-(SeCH2C6H4CH2Se)]}, and [(CO)6Fe2(μ-SeFe(CO)2cp)2]

Crystallographic and Structural Analysis of Iron Heterometallic Compounds Part IV: Heteropentameric Compounds

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The Chemistry of Iron Carbonyl Sulfide and Selenide Anions

Cited by 52 publications

References 1 publication

Structure and Electronic Properties of [Ni(dsdm){Fe(CO)3}2], an Unusual, Triangular Nickel Diiron Compound

Structure and Electronic Properties of [Ni(dsdm){Fe(CO)3}2], an Unusual, Triangular Nickel Diiron Compound

(Carbonyl)Iron-Selenolates: New Synthetic Methods and Reactions with Electrophiles. Crystal Structures of [(CO)6Fe2(μ-SeR)2]; R = Me3SiCH2 andp-O2NC6H4CH2, {(CO)6Fe2[μ-η2-Se,Se′-o-(SeCH2C6H4CH2Se)]}, and [(CO)6Fe2(μ-SeFe(CO)2cp)2]

Crystallographic and Structural Analysis of Iron Heterometallic Compounds Part IV: Heteropentameric Compounds

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Structure and Electronic Properties of [Ni(dsdm){Fe(CO)₃}₂], an Unusual, Triangular Nickel Diiron Compound

Structure and Electronic Properties of [Ni(dsdm){Fe(CO)₃}₂], an Unusual, Triangular Nickel Diiron Compound